Radical Polymerization in Industry
Peter Nesvadba
Performance Chemical Research, BASF Schweiz AG, Basel, Switzerland
1 INTRODUCTION
The goal of this article is to provide a brief overview
of radical polymerization (RP) in industry. It will
highlight the role of this technique in the context
of polymer industry and review its mechanistic and
process aspects from the point of view of industrial
polymerization. Then, recent progress in industrial
applications of controlled RP will be shown. Of
course, treatment of such a multifaceted discipline
as industrial RP (IRP) is possible only in very
limited depth. Therefore, only the most salient
features of IRP will be discussed and references
for further reading will be given. In accord with
the IUPAC recommendation,1 the term radical
polymerization will be used instead of free radical
polymerization.
Life as we know it would not be possible with-
out synthetic polymers, which are commonly called
plastics. The term plastics should not be confused
with the technical adjective plastic, describing per-
manent deformation of materials that were strained
beyond a certain point. Thus, plastics in this article
incorporate all synthetic polymers and macromolec-
ular materials, not only those undergoing plastic
(thermoplasts) or elastic (elastomers) deformation
but also highly cross-linked and hard thermoset-
ting polymers. Diverse semisynthetic macromolec-
ular materials such as vulcanized rubber, celluloid,
or galalith were discovered and already used in the
nineteenth century. However, the spread of poly-
mers to every aspect of modern life was possi-
ble only after the fundamentals of polymer science
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were laid down during 1920–1930.2,3 An account
of the history of polymers has been given by
Morawetz.4
The industrial production of several plastics
such as bakelite, polystyrene (PS), low density
polyethylene (LDPE), or poly(vinyl chloride) (PVC)
already started before World War II. However, only
the progress in science and technology and the
economic growth of the postwar period allowed
the worldwide production of polymers to grow at
around 9% per year, from 1.5 million tons (mt)
in 1950 to about 230 mt in 2009. Of these 230 mt,
55 mt was produced is Europe5 (Figure 1). In terms
of volume (m3 ), the production of polymers exceeds
that of iron and steel.
Globally, the long-term growth of plastics is
expected to be at around 4% and hence higher
than the gross domestic product (GDP) growth.
The average worldwide consumption5 of plastics is
significantly below that of the industrialized regions
(Figure 2), thus leaving room for future growth.
Up to 2015 and beyond, the fastest growth is
expected in Asia. One of the important stimulators
of the future demand for polymers is the growing
concern about climate change. In fact, more than
14% of all greenhouse gases worldwide are gen-
erated by the transportation sector. Reducing the
weight of cars through the replacement of met-
als by plastic can cut a vehicle’s weight by up
to 30%, resulting in a significant reduction in fuel
consumption. The proportion of plastics in a typ-
ical Western European car is about 15% today
(160 kg), compared with 6% in 1970. By 2020,
2 POLYMERS AND MATERIALS

Miot
300
2009: 230
250

200 2002: 200

150

1989: 100
100
1976: 50
50
1950: 1.5
0
1950 1960 1970 1980 1990 2000 2010

Figure 1 Worldwide production of polymers 1950–2009.

25.0%

20.0%

15.0%

10.0%

5.0%

0.0%
Am H
N x

a
to a

er a
a

B n

n
a

IS
lu

ly

K
ce
C

ic
es aft

c
Ea hin

pa

ai
an
si

U
Ita
EU ene
fri

C
er
fA

an

Sp
+
N

Ja
m
,A
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Fr
st

+
G

tin
R

La
e

er
dl

th
id

O
M

Figure 2 World production of polymers 2009, regional split.

plastics could account for more than 25% of a car’s
weight.6
Countless polymers are known in the literature,
but the number industrially manufactured poly-
mers is relatively small. For example in 2009, nine
types of polymers accounted for 77% (176 mt)6
of the 230 mt5 of polymers produced worldwide
(Figure 3). The five most important plastics are ther-
moplastic polymers, namely polypropylene (PP),
high density polyethylene (HDPE), linear low den-
sity polyethylene (LLDPE), LDPE, and PVC, of
which 143 mt were produced.
The rest are smaller volume polymers such
as polyesters, with poly(ethylene terephthalate)
(PET) as the most important example, PS as well
as engineering plastics, and high-performance
polymers. The latter exhibit superior mechanical
and thermal properties under a wide range of
conditions. As their name suggests, these are used
in the manufacture of parts or in applications
requiring extraordinary performance rather than for
construction, containers, or packaging, which is the
domain of commodity polymers. Some examples
of engineering plastics and high-performance poly-
mers are acrylonitrile–butadiene–styrene (ABS)
copolymers, polycarbonates (PCs), polyamides
(PAs), polyurethanes (PURs), polysulfones (PSUs),
polyetherketones (PEKs), polyetheretherketone
(PEEKs), polyoxymethylene (POM), polyimides
(PIs), polyphenylenesulfide (PPS), polyphenylene

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 RADICAL POLYMERIZATION IN INDUSTRY
Others 23% PP 19%
PC 2%
HDPE 13%
ABS 3%
PS 4%
PET 6%
LLDPE 8%
PVC 14% LDPE 8%
Total world 2009: 230 million tons
Figure 3 World’s largest volume polymers.
oxide (PPO), or fluoropolymers (e.g., Teflon,
polytetrafluoroethylene (PTFE), to name just
the most relevant. Additionally, there is the
important group of thermosetting polymers7–9
including epoxides, phenol-formaldehyde, urea,
and melamine polymers, as well alkyds and
unsaturated polyester resins. Last but not least,
must be mentioned the silicone-based10 polymers.
A special case is the family of dispersion11,12
polymers that have in common the same state
of aggregation but are diverse from the point
of view of their chemical composition. Lat-
est data on production volumes of individual
polymers and their regional split have been
published.13
The classes of polymers differ significantly not
only in their production volume but also in their
selling price,14,15 which is 0.5–2.5¤ kg−1 for com-
modity polymers, 10–12¤ kg−1 for PTFE or PSU,
and about 60¤ kg−1 for PEEK. Prices of high-tech
polymeric specialties, for example, those for the
electronic industry, are even much higher. As the
same polymer is often commercialized by differ-
ent companies under different names, a plurality of
trade names16 exists.
A number of good monographs17–21 and reference
works22–24 provide detailed information on indus-
trial polymers and their applications. Domininghaus
et al .14 provides a compilation of physical and tech-
nical data that are important for a professional selec-
tion of an optimal polymeric material for a given
application.
Synthetic polymers are prepared from low molec-
ular weight building blocks called monomers
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3
Polymerization
Chain-growth Step-growth
Radical Polycondensation
Coordination Polyaddition
Ionic
Figure 4 Mechanistic classification of polymerization
processes.
by a process known as polymerization. Existing
macromolecules can be further modified by polymer
analogous reactions. Polymerizations can be divided
from a mechanistic point of view2 into several
classes. RP belongs to the class of chain-growth
polymerizations (Figure 4).
Polymers produced by RP represent roughly
40–45% of all industrial polymers, which ranks
this method among the most important indus-
trial polymerization techniques. Polymers prepared
by nonradical processes are not discussed in
this article. Abundant literature is available on
ionic,25–29 step-growth,9, 29–31 coordination,29, 32–36
and group-transfer polymerization37 methods.
Nevertheless, it should be noted that there are
other industrially important polymer technolo-
gies and applications that are based on radical
processes. Thus, millions of tons of unsaturated
polyester resins9,31,38 are cured (cross-linked)
with radical initiators, predominantly peroxides.
The drying of alkyd resins39,40 also proceeds
via the radical mechanism. Photopolymerization
of coatings, printing inks, adhesives, and micro-
electronic components is a multibillion dollar
business and still rapidly growing. Radically
induced cross-linking41,42 of polymers, controlled
degradation43–45 of the molecular weight of
polypropylene, and modification of polyolefins
by grafting41, 46–48 of polar monomers are other
examples. Finally, radicals are very often involved
in the thermally and photochemically induced
degradation49,50 of polymers (e.g., in autoxidation)
as well as in the mode of action of the necessary
stabilizers51,52 used to prevent or retard this
deterioration.
4 POLYMERS AND MATERIALS

2 GENERAL AND MECHANISTIC ASPECTS n-butyl acrylate, 2-hydroxyethyl (meth)acrylate,

OF INDUSTRIAL RADICAL
POLYMERIZATION
The dominant position of RP in industry originates
from several unique characteristics that differenti-
ate it from other polymerization methods. Thus,
in contrast to ionic or coordination polymerization,
RP is tolerant of protic solvents and trace impuri-
ties such as oxygen or monomer stabilizers. Con-
sequently, it can be conducted in polar solvents
such as alcohols or, more importantly, water with
monomers that are not rigorously dried or puri-
fied. Furthermore, a large number of low-priced
monomers are available. Thus, from an economi-
cal point of view, RP is the technique of choice.
For example, the cost to polymerize styrene by
anionic polymerization is about 50% higher53 than
for RP.
2.1 Monomers
Many molecules containing unsaturated homo or
heteronuclear double bonds, dienes, trienes, strained
cycloaliphatics, exo-methylene-substituted cyclic
compounds, or vinylcyclopropanes are amenable2,54
to RP. However, the major industrial monomers are
compounds 1 (Scheme 1) containing C=C double
bond(s) where X is primarily X=H, (CH3 ) and
Y=H, Cl, COOH, COOR, CONH2 , CN, OCOCH3 ,
C6 H5 , –CH=CH2 ), which serve as precursors of
the corresponding polymers 2. Besides the basic
monomers that are produced on a very large scale,
there exists a variety of specialty monomers that
are used to make homopolymers or copolymers
with specific properties. Examples are the styrene
derivatives 1,4-divinylbenzene, p-vinylbenzyl
chloride, and p-acetoxystyrene, 4-vinyl pyri-
dine, N -vinyl pyrrolidone, various esters and
amides of acrylic and methacrylic acid (e.g.,
2-dimethylaminoethyl (meth)acrylate, glycidyl
methacrylate, N -isopropyl acrylamide), and a
variety of (meth)acrylates of polyhydric alco-
hols (e.g., ethylene glycol, trimethylolpropane,
or pentaerythrite). The latter, by virtue of their
high functionality, are used as cross-linkers. The
synthesis, properties, and applications of spe-
cialty monomers are summarized in the book55
by Havelka and McCormick. A compilation of
commercially available specialty monomers for
formulations cured by photopolymerization is
provided by Webster et al .56
The most important monomers along with the
applicable polymerization processes and typical uses
of the polymers are shown in Table 1.
Technological and economic information on the
industrial synthesis of monomers can be found in
the monograph of Arpe.57 The current raw mate-
rial base for monomers consists almost exclusively
of crude oil and natural gas and will remain so
also in the near future. It should be mentioned58
that only ∼4–8% of crude oil is used for poly-
mer production, the rest serving predominantly as
a source of energy. However, in view of the limited
availability and increasing price of oil and gas, a
shift59 to monomers and polymers from renewable60
resources, a renaissance of coal, as well as increas-
ing importance of chemical recycling58 of polymeric
materials is foreseeable.
2.2 Mechanism of Radical Polymerization
The mechanism of RP is now well understood
even though some problems such as control of
the stereochemistry of the propagation step or
sequence control61 are still not solved. On the
other hand, powerful techniques of controlled RP
have been developed in the last 20 years and
the first commercial applications are appearing.
A comprehensive treatment of the chemical and

Monomer Initiator Polymer

radical
X X X X X X
X I +M +M
I n
Y I Y Y Y Y Y Y
1 2

Scheme 1 Radical polymerization of a C=C monomer.

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 RADICAL POLYMERIZATION IN INDUSTRY 5

Table 1 Major monomers for industrial RP.

Monomer Polymerization technique

G B S E L P Use

Acrylic acid, acrylamide + V

Acrylic esters + (+) A,V
Acrylonitrile + F
Methyl methacrylate + + + + T
Ethene + + (+) (+) (+) F,T
Styrene + + (+) (+) T
p-Methyl styrene + + T
N -Vinyl pyrrolidone + + V
Vinyl acetate (+) (+) + (+) A,C
Vinyl chloride + (+) (+) + (+) T
Vinyl fluoride + C,T
Vinylidene fluoride + + C,T
Trifluorochloro-, tetrafluoroethene + T
Butadiene, chloroprene (+) + + A,C,E,T
Source: Table adapted from Ref. 2.  Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Polymerization in the gas-phase (G), in bulk (B), in suspension (S), in emulsion (E), in solution (L), by precipitation (P). Main use as adhesive (A), coating
(C), elastomer (E), fiber (F), thermoplastic (T), or various (V). + Mainly, (+) less often.

kd
Initiator cleavage I2 2 I Primary radicals
Initiation
ki
Chain initiation I + M I–M Initiating radicals

kp
Propagation Pn + M Pn + 1

ktr
Transfer Pn + T Pn + T
Chain
transfer k itr
Reinitiation T + M T–M

k tC
Termination Pn + m
Pn + Pm

k tD Pn= + PmH

I2 is initiator, M is monomer, Pn is a radical of chain length n,

T is a chain transfer species, Pn is a polymer

Scheme 2 Key mechanistic steps of radical polymerization.

mechanistic aspects of RP is provided by the
outstanding monographs54 of Moad and Solomon,
Matyjaszewski and Davis62 , and others63,64 (see
also Kinetics of Polymerizations). The mechanism
of RP consists of several steps as depicted in
Scheme 2.
The numerical values for important parameters of
RP are given in Table 2.
As the detailed discussion of this generally
accepted mechanism is available elsewhere, only
those points of industrial importance will be briefly
highlighted.

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6 POLYMERS AND MATERIALS

Table 2 General range of values for key parameters of radical polymerization.

kd = 10−4 −10−6 s−1 ki ≈ kp = 102 −104 M−1 s−1 ktC ≈ ktD = 106 −108 M−1 s−1
[I] = 10−2 −10−4 M [M] = 10−1 −10 M [R n ] = 10−7 −10−9 M
•

Source: Data from Ref. 65, p. 274.

Ph
+ +
H
Ph Ph
Ph
3 Initiation

Scheme 3 Mayo mechanism of styrene thermal autopolymerization.

2.3 Initiators and Initiation was proposed by Mayo. Thermal self-initiation of

Initiation of RP begins with the generation of
primary radicals (Scheme 2) from the initiator or
initiating system. Addition of the primary radicals
to the monomer then affords the initiating radicals.
The dissociation of the initiator is generally much
slower (kd ∼ 10−5 s−1 ) than the addition of primary
radicals to monomer molecules (ki ≈ 104 M−1 s−1 ).
A comprehensive discussion of all aspects of the
different classes of initiators or initiating systems
and the various kind of primary radicals (C, O, S,
Si, or P-centered) is provided in the monograph54 of
Moad and Solomon. A survey of radical initiators
including decomposition kinetics and half-life times
can be found in the handbook66 of Denisov and
coworkers and to a smaller extent in the Polymer
Handbook .67 Similar information on commercially
available initiators is accessible on the websites of
the major producers such as AkzoNobel, Arkema,
and Wako Chemicals. Braun recounts the origins
and development of RP from a historical point of
view.68 The most important initiators and initiating
techniques for industry are discussed briefly below
(see also Overview of Radical Initiation).
2.3.1 Thermal Autoinitiation
Styrene and its derivatives are the most prominent
examples of monomers that generate initiating
radicals by a purely thermal reaction without
participation of other reagents. For example, at
180 ◦ C, 80% conversion of pure styrene monomer
to polymer occurs in 40 minutes. The most accepted
mechanism69 of styrene autoinitiation involving
formation of a Diels–Alder adduct 3 (Scheme 3)
styrene is used industrially to prepare extremely
pure PS devoid of any initiator and derived
functional groups. Thermal autoinitiation of other
monomers (acrylates or methacrylates70 ) is much
slower and without any practical importance.
2.3.2 Azoinitiators
Industrially important azoinitiators are symmetri-
cal dialkyldiazenes 4 (Scheme 4) bearing tertiary R
groups with substituents (X) which serve to stabilize
the incipient radical, thus lowering the decomposi-
tion temperature. The most important member of
this class is azo-isobutyronitrile 5 (AIBN).
The thermal decomposition of azoinitiators gen-
erates two C-centered radicals and nitrogen. The
mechanism of the thermal and photochemical
decomposition of dialkyldiazenes has been reviewed
by Engel.71 Unfortunately, the yield of initiating
radicals is practically never quantitative. In fact,
depending on the viscosity of the surrounding media
and size of the primary radicals, the latter can
undergo an irreversible cage termination reaction
leading to inactive products. Hence, only those pri-
mary radicals that escape from the solvent/monomer
cage participate in chain initiation. This cage effect
negatively influences the initiator efficiency (f )
which is defined by (1) for an initiator generating n
(usually 2) primary radicals and typically72 lies in
the range of 0.5–0.7 (or 50–70%).
Rate of initiation
f = (1)
n × Rate of initiator decay
The cage termination products may be problem-
atic. For example, the dinitrile 6 formed from AIBN

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 RADICAL POLYMERIZATION IN INDUSTRY 7

R2 R2
N N
R1 N N R1
CN CN
X X
4 General formula 5 AIBN −N2 CN CN
of an azoinitiator
6 Highly toxic

N C
CN 7
R1, R2 = Alkyl groups +
X= CN, COOH, COOR, CN CN
8 Cage 8
amide, amidine
H +
CN 9 CN

Cage products
Initiation
8 CN

Scheme 4 Azoinitiators and their decomposition mechanism.

is a highly toxic compound,73,74 which prevents the
use of AIBN for making polymers that would come
into contact with foodstuff. The C–N dimer 7 can
redissociate75 into the radicals 8, thus complicat-
ing the polymerization kinetics. Furthermore, the
methacrylonitrile 9 is readily copolymerized with
the monomer and can influence76 the polymer prop-
erties.
The thermal decomposition of azoinitiators fol-
lows first-order kinetics (2), and the temperature
dependence of kd obeys Arrhenius law (3). A very
important characteristic of a polymerization initiator
is its half-life (t1/2 ) (4), which is the time required to
reduce the original initiator concentration by 50%.
It can be easily calculated using (2–4) and the tab-
ulated Arrhenius parameters A and Ea .
d[I]
− = kd [I]
d[t]
Ea
kd = Ae− RT
2 0.693
t1/2 = ln = (4)
kd kd
where kd is the rate constant of initiator decompo-
sition (s−1 ); [I] is the initiator concentration (M);
A is the Arrhenius frequency factor (s−1 ); Ea is
the activation energy for the initiator decomposi-
tion (J mol−1 ); R is 8.3142 J mol−1 K−1 ; T is the
temperature in K; and t1/2 is the half-life time (s−1 ).
Activation energies of thermal homolysis of
azoinitiators lie in the range of 100–170 kJ mol−1
and thus decomposition rates are very sensitive to
temperature. For example, t1/2 of AIBN decreases
from 10 hours at 65 ◦ C to 20 minutes at 90 ◦ C
and to ∼45 seconds at 110 ◦ C. In terms of volume,
AIBN is the most important azoinitiator. There are
several other initiators on the market with different
cleavage temperatures, solubility in water or organic
solvents, or functional groups (X) other than CN.
The latter allow introduction of the functionality into
the polymeric chain. Examples77 are compounds
10–14 shown in Scheme 5.
In general, advantage of azoinitiators over the
widely used peroxides is their lower tendency to
undergo chain transfer reactions. This leads to bet-
ter defined polymers containing fewer oxygenated
impurities, which enhances their thermal or photo-
(2) chemical stability.
(3)
2.3.3 Peroxides
Peroxides R1 –O–O–R2 are the most important
industrial radical initiators, exceeding the produc-
tion volume of azoinitiators by orders of magni-
tude. About 45% of the 207 000 tons of peroxides
that were utilized78 in 2007 by the worldwide plas-
tics industry was used to initiate RPs. The rest
found application in radically induced cross-linking

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8 POLYMERS AND MATERIALS

CH3O N
N HCl x N N
CN N CN
2 2 2

10 30 (Water) 11 44 (Water) 5 AIBN 65 (Toluene)

N N N
HO CN
N O 2 2 N O 2
H H

12 86 (Water) 13 88 (Toluene) 14 111 (Ethylbenzene)

Scheme 5 Examples of commercial azoinitiators with indicated temperatures (◦ C) for a half-life of 10 hours.

O O O
O O O O C3H7 O O
2 2 2

15 Dicumylperoxide 16 Dibenzoylperoxide 17 t-Butylperoxypivalate 18 Di-n-propylperoxy-

117 (Decane) 73 (Benzene) 58 (CCl2=CHCl) dicarbonate
50 (CCl2=CHCl)

O O t-Bu O
−
O OH HO O O O S O
2
O O t-Bu 2 O

19 t-Butylhydroperoxide 20 1,1-Di-t-butylperoxy- 21 Ethyl-methylketone 22 Persulfate anion

168 (Benzene) cyclohexane peroxide 69 (0.1 M NaOH)
97 (Dodecane) 105 (−)

Scheme 6 Examples of commercial peroxide initiators with indicated temperatures (◦ C) for a half-life of 10 hours.

of unsaturated polyester resins and polyethylene,
in controlled reduction of molecular weight of
polypropylene, and as synergists for flame retar-
dants. A detailed analysis of the markets, applica-
tions, and future trends for organic peroxides can be
found in the market study78 of Townsend Polymer
Services. The most important commercial perox-
ide initiators are dialkylperoxides, diacylperoxides,
hydroperoxides, peroxyesters, peroxydicarbonates,
peroxyketals, ketone peroxides, and inorganic per-
oxides. Several dozens of derivatives with varying
half-life, solubility, and volatility are available on
the market. Typical examples are the compounds
15–22 shown in Scheme 6.
The chemistry of peroxides was recently
reviewed.79 Generation of radicals from peroxides
occurs via homolysis of the weak –O–O– bond. The
bond dissociation energies66,80 of most peroxides
lie between 127 (dibenzoyl peroxide) and 211 kJ
mol−1 (H2 O2 ). The nature of the primary radicals
depends54 on the structure of the starting peroxide
and the type of cage reactions. For example, ther-
molysis of dibenzoylperoxide 16 gives rise to the
relatively long-lived benzoyloxy radicals 23. As 23
can also decarboxylate to give phenyl radicals 24,
both these radicals are involved in chain initiation.
The competitive irreversible coupling of 23 and 24
yields the cage products 25 and 26 (Scheme 7).
Analogously, hydroperoxides generate alkoxy
and hydroxyl radicals, and dialkylperoxides are
sources of alkoxy radicals. Aliphatic diacylperox-
ides yield predominantly alkyl radicals because of
the very fast in-cage decarboxylation of primary
aliphatic acyloxy radicals. However, the simple
homolysis of the –O–O– bond of peroxides is not the
sole decomposition mechanism. In fact, the radical
chemistry of peroxides is more complex than that
of azoinitiators. Diacyl peroxides are susceptible

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 RADICAL POLYMERIZATION IN INDUSTRY 9

O O
O O
16

O O
O O
O O
O + O
25
23 −CO2 23 23

Cage
24
26 24
Cage nonradical products Initiation

Scheme 7 Thermal decomposition of dibenzoyl peroxide.

O O O O
O O O R + O

16 R
(a)
O O O + O
−
O O O N + O

16
O CH2
N −H+
O + N+ N
27
(b)
Initiation

Scheme 8 Induced decomposition of dibenzoyl peroxide with (a) radicals and (b) aromatic amines.

to radical-induced decomposition resulting from O O O

homolytic attack of a radical on one of the oxygens −O −
S O O S O− 2 O S O
of the –O–O– bond (Scheme 8). The consequence is O O O
22 28
chain transfer from the growing chain to the initiator
with the concomitant incorporation of a benzoyloxy Scheme 9 Radical generation from a persulfate.
group into the polymer in a form of a secondary
ester. Such end groups may negatively influence the
thermal (PS76 ) or hydrolytic (PVC81 ) stability of the the room-temperature curing9,31,83 of unsaturated
polymer. Of practical importance is the decomposi- polyesters.
tion of dibenzoyl peroxide 16 induced82 by aromatic The water soluble sodium, potassium or ammo-
amines (Scheme 8). As this reaction takes place nium salts of peroxydisulfuric acid (persulfates)
already at room temperature or even below, addition are important initiators for aqueous and emulsion
of an amine synergist (often called accelerator) to (EP) polymerizations. The mechanism of radical
a polymerizable composition containing 16 allows generation from the persulfate dianion 22 depends
the polymerization to occur at room temperature on pH. Homolytic cleavage affording the sul-
or even around 0 ◦ C. Two-component initiating fate radical anion 28 dominates in neutral media
systems consisting of 16 and N , N -dimethylaniline (Scheme 9) whereas heterolytic cleavage occurs in
27 (or similar derivatives) are widely used for acidic solution.

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10 POLYMERS AND MATERIALS

−
O O O O O O
− − − − −
O S O O S O + O S O S O + O S O + O S
O 22 O OH O O OH
(a)
−
R– OOH + Co2+ R– O + HO + Co3+
+
R– OOH + Co3+ R– OO + H + Co2+
(b)

Scheme 10 Redox reaction between (a) persulfate and hydrogen sulfite, (b) hydroperoxide and Co ions.

Furthermore, redox reactions occur between
persulfates 22 and reducing agents such as
2-mercaptoethanol, thiourea, sulfites,84 amines,
dithionites, or thiosulfates. Such initiating systems
are frequently employed in aqueous EPs. In
addition to the amine–dibenzoylperoxide system,
the redox reaction of hydroperoxides with ions of
various transition metals (mostly Co or Mn) is
commonly used for the room-temperature curing of
unsaturated polyesters. Typically, two-component
initiating systems consisting of a hydroperoxide
(e.g., cumyl hydroperoxide or ethylmethylketone
peroxide 21) and a Co- or Mn-based accelerator
(e.g., cobalt octoate or manganese naphthenate) are
used for this purpose (Scheme 10).
Redox-initiated polymerizations were reviewed85
by Misra and Bajpai. A comprehensive discussion
of the initiating mechanism of the different peroxide
families is available in the monograph54 of Moad
and Solomon.
Organic peroxides, as well as azoinitiators, are
unstable compounds and decompose exothermally at
relatively low temperatures. They must be handled
and stored properly and most require some form
of temperature control. Guidelines for the safe
handling of these initiators were recently reviewed86
and are available on the web pages87 of their
manufacturers.
2.3.4 Miscellaneous Radical Initiators
Peroxides are the most important industrial initia-
tors for RP followed by azoinitiators. Much smaller
volumes of specialty initiators are also used.
One example is 2,3-dimethyl-2,3-diphenyl butane,
known as Perkadox 30 (AkzoNobel), used in
styrene polymerization. This C–C dimer thermally
dissociates into cumyl radicals (t1/2 = 1 hour at
259 ◦ C in PhCl). Novel initiators88 with improved
handling and storage stability as compared to
peroxides or azo-compounds are highly desirable
and are slowly appearing on the market. Examples
are sterically hindered N -acyloxyamines89 29
and silylated benzopinacol90 derivatives 32
(Scheme 11). The proposed mechanism of action of
the N -acyloxyamine radical initiators 29 involves91

O
R1 N O Heat
R1 N + R2
R2
O
O
29 30 31

Heat
R3Si O O SiR3 R3Si O + O SiR3

32

Scheme 11 N -Acyloxyamine and silylated benzopinacol initiators.

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 RADICAL POLYMERIZATION IN INDUSTRY
homolysis of the N–OC bond to generate N -aminyl
radicals 30 and acyloxy radicals 31. This contrasts
with the NO–C bond homolysis of alkoxyamine
initiators for controlled RP.
Initiators for controlled RP are discussed in
respective sections.
2.3.5 Photoinitiators
Photoinitiators92–95 are compounds that generate
primary radicals upon irradiation with light of a
suitable wavelength (generally UV).
They are niche products used to ini-
tiate polymerization (curing) of radically
polymerizable/cross-linkable coatings (e.g., on
furniture, flooring, metal, plastics, automotive parts,
paper, optical fibers), printing inks, and adhesives,
or in the production of microelectronic devices.
They are not used, however, in the production
of bulk, large-volume polymers. Radiation curing
in a broader sense96 also encompasses curing
initiated by electron beam97 (EB) or cationic92
photoinitiators, but these topics are not treated
here.
A UV-curable formulation97 for a coating, ink,
or adhesive consists of a mixture of (i) 30–50%
specialty monomers or oligomers,56 which impart
most of the basic properties to the final cured or
cross-linked material; (ii) 10–40% reactive diluents
or monomers, which permit the adjustment of for-
mulation viscosity and crosslink the oligomer; (iii)
1–20% additives and pigments; and (iv) 0.5–8%
photoinitiators which provide the initiating radicals.
Functionally terminated low to medium molecular
weight polymerizable oligomers are the backbone
of UV-curable coatings and determine properties
of the cured coating: for example, hardness, chem-
ical resistance, and flexibility. Commonly used
oligomers include acrylates of polyhydric alco-
hols, oligomeric diols, and polyols having epoxy-,
urethane-, polyester-, or siloxane backbones. Of
less importance are the unsaturated polyesters or
thiol–ene systems. Oligomers based on methacry-
lates are sometimes used in combination with acry-
lates in order to improve thermal resistance and
mechanical hardness of the finished coating.
UV-light-triggered radiation curing provides sev-
eral advantages over thermal curing, which include
(i) very rapid cure occurring within seconds,
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11
(ii) ambient temperature curing which permits the
coating of heat-sensitive substrates such as wood
and plastics, (iii) more efficient, compact operations,
(iv) zero or low solvent levels, and (v) good film
properties and performance. Among the drawbacks
of UV curing is the high sensitivity toward oxygen
inhibition, the impossibility to cure thick pigmented
layers, and the difficulty to cure three-dimensional
objects (shadow zones). Details on equipment for
UV and EB curing (lamps, electron guns, machin-
ery) can be found in the monograph98 of Mehmert
and coworkers. A comprehensive overview of pho-
topolymerization in polymer science and technology
is provided in the four-volume compendium99–102 of
Fouassier and Rabek, and Marrion reviews103 the
chemistry and physics of coatings.
The market study by SRI Consulting104 pro-
vides a detailed analysis of the global market for
radiation-curable products. In 2007, the market vol-
ume was estimated at 390 000 metric tons with an
average growth of 4–5% per year.
Radical photoinitiators92–95 are generally divided
into two classes. Compounds undergoing homolytic
bond cleavage (Norrish I cleavage) upon irradiation
are termed type I photoinitiators. Typical examples
are α-hydroxyketones 33–34, α-aminoketones 35,
benzil dialkylketals 36, acylphosphine oxides 37,
and bisacylphosphine oxides 38 (see Scheme 12).
The oxime esters (e.g., 39) photoinitiators95,105,106
were developed for highly specialized applications
in electronics such as photocuring of color filter
resists and the black matrix resin of liquid crystal
displays.
Type II photoinitiators, on the other hand, interact
in their excited state with a second molecule
(coinitiator) to generate radicals in a bimolecular
reaction (Scheme 13). Derivatives of benzophenone
40 and thioxanthone, for example 41, are the
most important type II photoinitiators. Amines
such as N -methyldiethanolamine, triethanolamine
42, and esters of 4-dimethylamino benzoic acid
are typical examples of coinitiators. The resin
matrix itself can also act as a coinitiator if it
possesses easily extractable hydrogen atoms. Alkyl
phenylglyoxylates 43 are also considered107 as type
II photoinitiators. A compilation of commercially
available photoinitiators and a discussion of their
chemistry and applications is provided in the book
by Dietliker.93
One of the biggest challenges95 for the future
growth of the UV market is the development of
12 POLYMERS AND MATERIALS

Light Norrish I cleavage

PI PI* R1 + R2

Photoinitiator Excited photoinitiator Primary radicals

(a)

Photochemically cleavable bond

OH O
OH O N N
O O O O
O

33 34 35 36

O
O O
P P N
O O O N O O

(b) 37 38 39

Scheme 12 (a) Type I photoinitiators and (b) some of their representative examples.

O H
*T HO HO OH
O O
HO HO OH
Light H N
42
+
Electron and N
40 proton transfer

O O Initiation Initiation or dimerisation

O
Alkyl
S O

41 43

Scheme 13 Type II photoinitiators.

nonextractable, odorless, and low-migration pho-
toinitiators. Such products will be applicable in
coatings destined for indirect food contact. So far,
few UV-curable systems are present in this mar-
ket because the photoinitiator or its fragments can
migrate into foodstuffs.
2.4 Propagation
Propagation is the repeated addition of the growing
macroradical to monomer. The rate constants
of propagation are typically in the range of
kp ∼ 102 −104 M−1 s−1 . The magnitude of kp
depends slightly on the degree of polymerization
Xn of the macroradical, at least for the first (∼10)
propagations steps. The mechanistics aspects of the
propagation step of RP are well understood54,62,63
and need not to be discussed here. However, one
should note that the simplified picture of a 100%
regiospecific head-to-tail addition (Scheme 1)
which is shown in many introductory texts on
polymerization is not completely correct. In fact,
head-to-head addition is observed in polymeriza-
tions of most monomers. For example, it occurs
to the extent of 11% in the polymerization of allyl
esters108 (Scheme 14).

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 RADICAL POLYMERIZATION IN INDUSTRY 13

X X X X X
Tail Head Tail addition
M
CH2 CH2 CH2 CH2 CH2
Y Y Y Y Y
X X
CH2 + H2C
X X X X X
Y Y
1 CH2 CH2 M
CH2 CH2 CH2
Y Y Y Y Y
Propagating radical Monomer Head addition

Head-to-head linkage Tail-to-tail linkage

Scheme 14 Regiosequence isomerism—head versus tail addition.

I O
O
O O I O O
I 44 n
Ph Ph O O O
O O O O
O O O
Ph
44 45 Ph

Scheme 15 Ring-opening polymerization of a cyclic monomer.

Of course, even more variations are observed
with diene (1,3-butadiene, isoprene, chloroprene)
monomers. It should be noted in this context that
even the addition of primary radicals (Scheme 2)
to monomers 1 is not always regioselective. For
example, in the reaction of benzoyloxy radicals 23
with styrene109,110 tail addition (80%), head addition
(6%), and addition (in end effect substitution) to
the styrene benzene ring (14%) can be observed.
Deliberate synthesis of head-to-head polymers and
their properties were reviewed111 by Vogl and
coworkers.
Propagating organic radicals are more or less
planar (sp2 hybridized) and, consequently, the
polymers formed by RP are generally atactic.
Detailed treatments of the stereochemical aspects of
the propagation step in RP are available.54,62
In general, polymers produced by RP have
higher densities than the starting vinylic monomers.
As a consequence, polymerization is accompa-
nied by volume contraction (up to 20% depending
on monomer), which can be a significant prob-
lem in adhesive, coating, mold-filling (dental fill-
ings), and other applications where volume change
(shrinkage) is undesirable. However, only very
low shrinkage or even a net increase in volume
is observed with special cyclic monomers2,54,112
undergoing radical ring-opening polymerization
(ROP). Each propagation step of ROP results in
ring-opening. For example, the ROP of the bicyclic
2-methylene-l,3-dioxepane 44 (Scheme 15) occurs
with a small (0.5%) volume expansion. This expan-
sion is probably due to the conversion of the more
dense structure of the crystalline monomer 44 into
the less dense structure of the amorphous polymer
45.113
At low conversion, the overall rate of polymer-
ization Rp is kinetically first order in monomer and
half order with respect to initiator (5), for definition
of f see (1).


d[M] kd 1/2
Rp = − = kp f [M][I]1/2 (5)
dt kt
The kinetic chain length ν (6) is defined as the
average number of monomer molecules polymerized
by each initiating radical. It can be expressed as the
rate of chain propagation divided by the sum of the
rates of all of the chain termination processes. In the
case of termination by disproportionation, it equals
the number average degree of polymerization X n .
kp [M]
ν= (6)
2(fkd kt [I])1/2
Equations (5) and (6) show that increasing the
concentration of the initiator will indeed increase

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14 POLYMERS AND MATERIALS

the rate of polymerization, although not linearly, but = Monomer A = Monomer B

will inevitably result in a polymer of shorter chain
length. Statistical copolymer
The propagation step is potentially a reversible Alternating copolymer
process. Polymerization can occur spontaneously
only when the associated free-energy change Gp Gradient copolymer
is negative. Gp is expressed in (7) where Hp Block copolymer
represents the enthalpy and Sp represents the
Graft copolymer
entropy change upon propagation.

Gp = Hp − T Sp (7)

Figure 5 Different types of copolymers.
Each monomer can be characterized by a ceiling
temperature Tc at which, for a given monomer
k pAA
concentration, the polymerization rate becomes PA + M A PA
k pAA
zero. k pAB rAB =
Common monomers such as ethene, vinyl acetate, PA + M B PB k pAB

and acrylates have very high Tc ’s (>400 ◦ C) and k pBB

depropagation does not occur under viable poly-
merization conditions. Styrene has a significantly
lower ceiling temperature and depropagation must
be taken into account above 250 ◦ C. The addi-
tion of a substituent to the α position of a vinylic
monomer greatly reduces Tc . α-Methylstyrene can,
for example, be polymerized only at room temper-
ature or below.
2.5 Copolymerizations
Copolymerization of two or more monomers by RP
is commonly used in industry to tune the properties
of commercial polymers. For example, addition of
the polar monomer acrylonitrile to styrene affords
a copolymer with much improved oil and grease
resistance. Many industrial polymers are prepared
from two, three, or even more monomers. In addi-
tion to varying chain length and stereochemistry,
copolymers differ in their composition (the rela-
tive amounts of each monomer incorporated into the
copolymer), sequence distribution (the way in which
these monomer are arranged within the chain), and
architecture (linear or graft or branched) (Figure 5).
Different monomers lead to different radicals,
and the relative rates of propagation depend on the
steric and electronic properties of both monomer
and radical. Therefore, at any given time the
ratio at which the monomers are incorporated
into the polymer is not equal to their ratio in the
monomer mixture. Hence, both the composition
PB + M B PB k pBB
rBA =
k pBA
k pBA
PB + M A PA
Scheme 16 Copolymerization of two monomers MA and MB .
of the monomer feed and copolymer will change
with conversion and, consequently, batch copoly-
mers will in most cases not have homogeneous
composition at the molecular level.
Several kinetic models of radical copolymeriza-
tion have been developed (e.g., terminal, penulti-
mate, complex dissociation, and so on) and details
can be found in the monographs of Matyjaszewski
and Davis62 or Moad and Solomon.54 Here, only
the simplest, the so-called terminal model114 of rad-
ical copolymerization, will be briefly discussed. This
model describes the copolymer composition for the
majority of systems reasonably well but is less suit-
able for copolymerization kinetics, for which the
penultimate model is more appropriate.
The terminal model assumes that the reactivity of
the polymer radical depends only on the nature of its
terminal monomer unit: that is, the penultimate unit
on the macroradical does not affect its reactivity.
Accordingly, the kinetics of copolymerization of
two monomers MA and MB is determined by
the relative rates of four propagation reactions
characterized by four propagation rate constants
kpAA , kpAB , kpBB , and kpBA (Scheme 16).
The composition of a copolymer formed at a
given instant from a specific monomer mixture is

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 RADICAL POLYMERIZATION IN INDUSTRY
Table 3 Selected terminal model reactivity ratios.
Monomer MA
Methyl methacrylate
Styrene
Styrene
Vinyl chloride
Vinyl acetate
Source: Data from Ref. 67.
described by the Mayo–Lewis equation114 (8):


FA fA rAB fA + fB
= (8)
FB fB fA + rBA fB
where FA = (1−F B ) and fA = (1−f B ) are the
instantaneous mole fractions of monomer MA in the
polymer and in the monomer mixture, respectively,
and rAB = kpAA /kpAB and rBA = kpBB /kpBA are the
monomer reactivity ratios.
Using this equation, it is possible to predict the
copolymer composition for a given monomer mix-
ture from just two parameters, namely, the reactiv-
ity ratios (sometimes also called copolymerization
parameters) rAB and rBA , which are available for
many monomers.67 However, the published data
often spans a considerable range. Additionally, sev-
eral empirical methods54 for the prediction of reac-
tivity ratios are available, the most widely used
being the Q–e scheme115,116 of Alfrey and Price.
A few values of the reactivity ratios are given in
Table 3 for illustration.
As seen from Table 3, the values of rAB and
rBA are generally different. The special case where
rAB = rBA = 1 occurs with monomers that are very
similar, such as the homologous esters of acrylic or
methacrylic acids. For this case, the product is a ran-
dom copolymer and the monomers are incorporated
into the copolymer according to their proportions in
the monomer mixture. In cases where rAB < 1 and
rBA < 1, a tendency toward alternation is observed
because cross-propagation is favored over homo-
propagation. When rAB and rBA approach zero, an
alternating copolymer is obtained. A well-known
example is the styrene–maleic anhydride copoly-
mer. The situation where rAB and rBA are both
greater than 1 is rare, and copolymers with larger
blocks consisting of MA and MB are the result. In
cases where rAB < 1 and rBA < 1 (or rAB > 1 and
rBA > 1), there always exists exactly one so-called
azeotropic composition of the monomer mixture at
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15
Monomer MB rAB rBA
Ethyl methacrylate 1.0 1.0
Acrylonitrile 0.4 0.05
Maleic anhydride 0.02 0.01
Vinyl acetate 2.0 0.3
Styrene 0.05 50.0
which the composition of the formed copolymer
is the same as that of the monomer mixture. The
azeotropic composition is given by (9).
[MA ]Azeotrop 1 − rAB
= (9)
[MB ]Azeotrop 1 − rBA
Its existence is of significant industrial
importance. In fact, a copolymer without composi-
tional heterogeneity can be prepared by conducting
simple batch copolymerization if the ratio of both
monomers fulfills (9). Analogous composition
equations117,118 for (rare) azeotropic composition of
three or four monomers have also been developed.
Finally, when rAB > 1 and rBA < 1 (or rAB < 1
and rBA > 1), one monomer will always be pref-
erentially incorporated into the copolymer. These
copolymerizations have no azeotropic composition.
Of course, kinetic treatment of ternary54 (three
monomers) or even quaternary (four monomers)
copolymerization is significantly more complicated.
For example, nine distinct propagation reactions and
six reactivity ratios must be considered in the ter-
minal model for three monomers.
2.6 Chain Transfer and Chain Transfer Agents
A chain transfer reaction is the interaction of the
propagation radical with a nonradical species (T)
to produce a dead polymer chain and a new rad-
ical (T∗ ) capable of initiating a new propagating
chain (refer Scheme 2). Details on the theory can
be found in the article119 by Chieftain and Gizzard
or that by Corner.120 In principle, chain transfer can
occur with any species present in the polymeriz-
ing system (initiator, solvent, monomer, polymer,
adventitious impurity, or deliberately added chain
transfer agent) and it always causes a reduction in
X n , the number-average degree of polymerization.
16
Table 4 Transfer constants (ktr /kp ) at 50 ◦ C.
Styrene
Benzene 2 × 10−6
Toluene 1 × 10−5
Ethyl acetate 5 × 10−4
CCl4 1 × 10−2
1-Butanthiol 20
Source: Data from Ref. 67.
Furthermore, chain transfer to the polymer results in
branching or potentially cross-linking. For example,
intramolecular chain transfer (backbiting) leading to
branching is observed during the RP of ethylene.121
Quantitatively, the efficiency of chain transfer to a
given species is characterized by its transfer constant
Ctr = ktr /kp . For efficient chain transfer to occur,
the rate constant of reinitiation (kitr ) by T∗ must be
equal to or greater than that for propagation (kp )
(refer Scheme 2). The magnitude of the transfer
constant depends on the structure of both the trans-
fer agent and the radical. Since the propagation and
transfer reactions show similar temperature depen-
dence, chain transfer constants change only slightly
with temperature. The transfer constants for variety
of monomers and transfer agents can be found in
the literature.67 Most organic compounds have low
transfer rates, and transfer is important only when
they are present in high concentration, that is, as
solvent. Table 4 illustrates the Ctr values for a few
typical solvents and chain transfer agents at 50 ◦ C.
Deliberately added chain transfer agents (T) with
large Ctr are often used in industrial polymerizations
to control (limit or reduce) the molecular weight
and molecular weight distribution of polymers. The
influence of chain transfer on X n can be described
by the Mayo equation122 (10):
1 1 [T]
= + CtrT
Xn X n0 [M]
where X n , X n0 are the number-average degree of
polymerization in the presence or absence of chain
transfer, respectively, and CtrT is the chain transfer
constant of T.
The added transfer agent is said to behave ideally
if its chain transfer constant is equal to unity.
In this case, the ratio of the rates at which the
monomer and transfer agent are consumed by the
growing radicals is constant and equal to the ratio
of the molar concentrations of the monomer to
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POLYMERS AND MATERIALS
Methyl acrylate Methyl methacrylate Vinyl acetate
2 × 10−5 4 × 10−6 1 × 10−4
1 × 10−4 2 × 10−5 2 × 10−3
6 × 10−5 1 × 10−5 2 × 10−4
2 × 10−4 2 × 10−4 0.8
1.5 0.6 50
transfer agent. This means that X n remains constant
throughout the polymerization. On the other hand,
a transfer agent with CtrT  1 will be rapidly
consumed in early stages of the polymerization. In
the case of CtrT  1, the ratio [T]/[M] increases
with conversion, leading to a decrease in X n as
the polymerization progresses. Polymers with a
broad molecular weight distribution result in both
cases. Continuous addition of the monomer or
transfer agent during polymerization to maintain a
constant the [T]/[M] ratio may help to overcome
these problems. The control of the molecular
weight of the polymer with the transfer agent
translates into control of the viscosity of the reaction
mixture and, through mitigation of the gel or the
Norrish–Trommsdorff effect,123,124 into control of
the polymerization rate and exothermicity.
Typical chain transfer agents used in industrial
synthesis of variety of polymers (PS, poly (methyl
methacrylate) PMMA, ABS, acrylic-, styrene-
butadiene-, or acrylonitrile-butadiene copolymers)
include mercaptans such as n-octyl mercaptan, n-
dodecyl mercaptan, or 2,2-dimethyldecyl mercaptan
(tert-dodecyl mercaptan). Technical information125
on mercaptans, as well as examples126 of their
use as chain transfer agents, can be found on
the web site of their producers. Chain transfer
with n-dodecyl mercaptan 46 in the styrene
polymerization is exemplified in Scheme 17.
(10)
Primary mercaptans are more active chain trans-
fer agents than secondary or tertiary ones. Apolar
mercaptans are lipophilic and odiferous compounds
of moderate toxicity. Examples of water-soluble
and practically odor-free chain transfer agent
are mercaptoacetic acid (thioglycolic acid) and
2-mercaptoethanol. Moreover, these agents intro-
duce functionalities (COOH or OH) into the chains
providing access to monofunctional120,127 polymers.
A special case of chain transfer is the reversible
addition fragmentation chain transfer (RAFT),
which is an important method of controlled RP
 RADICAL POLYMERIZATION IN INDUSTRY 17

ktr H
+ C12H25 SH + C12H25 S Chain transfer
Ph 46 Ph

kitr + St Reinitiation
+ C12H25 S C12H25S C12H25S
Ph Ph Ph Ph

Scheme 17 Polymerization of styrene with chain transfer with n-dodecylmercaptan.

(see Reversible Addition Fragmentation Chain Macroradicals can also terminate by reaction with
Transfer (RAFT) Polymerization: Mechanism, radicals derived from the initiator. Finally, another
Process and Applications). very important source of termination reactions is
the deliberately added molecules called inhibitors
or oxygen (oxygen inhibition).
2.7 Chain Termination

The propagating radicals in RP add a monomer 2.7.1 Inhibitors

unit every ∼1 ms on average and typically termi-
nate after about ∼1 s. Polymeric chains with high
X n are formed during this short time. Termination of
growing radicals occurs via coupling (ktC ) or dispro-
portionation (ktD ) (Scheme 18). The corresponding
rate constants are very high, kt ∼ 107 −109 M−1 s−1 ,
approaching the diffusion-controlled limit.
Sterically undemanding radicals terminate prefer-
entially through coupling (styrene), whereas radicals
derived from 1,1-disubstituted monomers generally
undergo disproportionations (methyl methacrylate).
The self-termination of growing macroradicals is a
diffusion-controlled process. Therefore, the termi-
nation rate constants depend strongly on the chain
lengths, and kt decreases with increasing viscosity
of the polymerizing mixture. The increase of vis-
cosity in bulk polymerizations at medium to high
conversions slows down the movement of large
chains to such a level that their self-termination
becomes very slow. On the other hand, monomer
molecules may still diffuse rapidly. As a conse-
quence, an autoacceleration phenomenon known as
the Norrish–Trommsdorff or gel effect123,124 may
occur.
Pure monomers must be protected during storage
from polymerization by mixing them with small
amounts of polymerization inhibitors, species able
to rapidly and efficiently scavenge propagating
and/or primary radicals. Moreover, the presence of
inhibitors is also necessary during the synthesis and
purification (e.g., distillation) of monomers. In fact,
a distinction between storage and in-process stabi-
lizers is sometimes made. An ideal inhibitor will
prevent polymerization during what is termed an
induction period . Once consumed, polymerization
proceeds at a normal rate. Species that do not show
a distinct induction period but rather slow down
polymerization are called retarders. This topic was
reviewed by Bovey and Kolthoff128 and Tüdos
and Földes-Berezsnich.129 Common inhibitors
include stable radicals such as galvinoxyl, nitroxide
radicals, diphenylpicrylhydrazyl, phenols, quinones,
nitrones, nitro and nitroso compounds, phenoth-
iazine, and salts of transition metals which can trap
C-centered radicals by electron transfer. Examples
of industrially important inhibitors (Scheme 19) are
p-methoxyphenol 47, 2,4-di-t-butyl catechol 48,

Combination CH2 CH CH CH2

ktC Ph Ph
CH2 CH CH CH2
+ ktD
Ph Ph
CH CH + CH2 CH2
Disproportionation
Ph Ph

Scheme 18 Termination of polystyrene macroradicals by combination and disproportionation.

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18
OH
OH
OH
S N
N N
H OH
OMe
47 48 49
Scheme 19 Examples of polymerization inhibitors.
HO
O2 47
O O
X kO2
X
Peroxidation 54
Scheme 20 Inhibition of polymerization with p-methoxyphenol.
phenothiazine 49, N , N -diethylhydroxylamine 50,
salts of N -nitroso phenylhydroxylamine 51, and
4-hydroxy-TEMPO 52. An example of a retarder is
2,6-di-t-butyl-7-phenyl quinone methide 53, which
is used in combination with nitroxide radicals as a
storage stabilizer130 for radiation-curable coating or
ink compositions.
The phenolic inhibitors 47–48, which are used
mostly as storage stabilizers, require131,132 traces of
oxygen in order to be fully effective. The phenols
themselves are rather poor scavengers of C-centered
radicals. The latter, however, react very rapidly
with oxygen, affording peroxy radicals 54 which
are efficiently transformed into nonradical products,
namely, hydroperoxides 55 and cyclohexadienones
56, by reaction with phenols (Scheme 20).
For this reason, the oxygen content in large stor-
age tanks containing acrylic or methacrylic acid and
p-methoxyphenol (100–200 ppm) as polymerization
inhibitor is continuously monitored and maintained
at a specific level. An illustrative case of a runaway
acrylic acid polymerization caused by insufficient
inhibition was reported133 by Levy and Penrod.
On the other hand, phenothiazine 49 is a good
hydrogen donor to both C-centered and peroxy
radicals and, therefore, an excellent inhibitor132,134
even in the absence of oxygen.
The liquid and rather volatile (bp 125 ◦ C)
N, N -diethylhydroxylamine 50 is used as in-process
inhibitor in distillations of monomers such as
styrene, divinylbenzene, isoprene, and butadiene.
In precise laboratory work with monomers, the
inhibitors are often removed by distillation, by
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POLYMERS AND MATERIALS
OH
N=O
O-]3 Al O
N H
O
50 51 52 53
O OMe ROO
OMe
OMe
O
O O H
OO R
X 55 56
filtration over a pad of aluminum oxide, or by a
suitable extraction procedure. In industrial polymer-
izations, such purifications would be too expensive.
Therefore, in most cases, the inhibitor is not
removed but consumed by the additional initiator.
2.7.2 Oxygen Inhibition
RPs are tolerant to protic solvents but suffer from
oxygen inhibition when conducted in air-saturated
media or under an air atmosphere. The dioxygen
molecule, due to its biradical ground state character,
reacts with carbon-centered radicals to give peroxy
radicals 54. The rate of this peroxidation reaction
is much greater135 (kO2 ∼ 108 −109 M−1 s−1 ) than
the typical rates54 of propagation (kp ∼ 102 −104
M−1 s−1 ). Hence, at equal monomer and oxygen
concentrations, the peroxidation would be 104 −107
faster than propagation (Scheme 21). The concen-
tration of dissolved oxygen in monomers is on
order136 of 10−3 M, whereas the concentration of
monomers is generally in the range of 0.1–10 M.
Even so, the vast majority of carbon-centered radi-
cals in air-saturated monomers are converted into
the peroxy radicals 54. The latter add only very
sluggishly137 (kOO ∼ 0.1−3 M−1 s−1 ), in what is
now a rate-determining step, to monomers afford-
ing new C-centered radicals. As these C-radicals
react again preferentially with oxygen, the result
is an alternating copolymer with oxygen. The nor-
mal polymerization will be possible only when the
majority of dissolved oxygen is consumed. This can
 RADICAL POLYMERIZATION IN INDUSTRY
X
X X
kp
O2 O O
X kO2 X 54
Peroxidation
Scheme 21 Oxygen inhibition.
occur if the rate at which it is replenished from the
air-exposed surface is sufficiently low. The oxygen
copolymers are polymeric peroxides that are ther-
mally and photochemically unstable and thus impair
the properties of the final polymer. Moreover, per-
oxy radicals138 abstract H atoms from the surround-
ing substrates (PH) to yield new radicals and the
hydroperoxides 55. The latter are potential sources
of new radicals, which may further complicate the
polymerization.
The influence of oxygen on radical and other
polymerizations has been reviewed by Bahanu and
Kishore.139 To prevent these detrimental effects,
measures must be taken to exclude oxygen by
conducting the polymerization under vacuum or
nitrogen, or in a refluxing solvent. Oxygen inhi-
bition is a serious problem and is much more
difficult to avoid in the photopolymerization of
thin films and coatings due to the very large sur-
face. Here, it leads to incompletely cured, tacky
surfaces with poor mechanical properties. Differ-
ent methods to overcome oxygen inhibition in
these applications were reviewed140 by Scran-
ton and coworkers. Latest strategies involve an
admixture of oxygen-scavenging additives,141,142
use of monomers with high functionality,143 or
singlet oxygen144 sensitizers. It should be noted
that oxygen inhibition is not a problem for every
RP process. The radical thiol–ene click reaction,
which is becoming an important tool for polymer
synthesis,145–147 is much less sensitive to oxygen.
3 POLYMERIZATION PROCESSES
3.1 General Comments
Rather than listing the complete literature dealing
with industrial polymerization processes and the
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19
X O O
O O O2 O O
kOO X X
X X
P–H
O O H
+ P
X 55
related reactor technology, we refer the reader to
good introductory texts.148–150
Industrial polymerizations differ from the
processes used for synthesis of low molecular
compounds in several respects. For one, it is
usually not possible to purify the final polymer by
standard distillation or crystallization techniques.
Polymers obtained by classical RP are always
mixtures of macromolecules with varying degrees
of polymerization and deviation from the idealized
structure. Separation of these mixtures is not
possible on an industrial scale. Elimination of
residual monomers, initiators, or solvents can also
be a difficult and costly task requiring special
methods and equipment.
The properties of the polymer, for example,
its molecular weight distribution which influences
its mechanical properties and processability, often
strongly depend on the method (e.g., suspension
polymerization or EP) by which it is prepared.
An important feature of polymerization in solu-
tion or in a melt is the dramatic increase, often
by several orders of magnitude, of the viscosity
during the reaction. This viscosity increase is the
cause of the autoacceleration effect called the Nor-
rish–Trommsdorff effect.123,124 It complicates mix-
ing and pumping of the reaction mass and signifi-
cantly reduces the rate of heat transfer and, there-
with, the efficiency of the reactor cooling. Temper-
ature control of industrial polymerizations is a very
critical task because of the highly exothermic nature
of RPs. In many cases, a rapid and, therefore, almost
adiabatic runaway polymerization would cause tem-
perature increase of many hundreds of degrees,151
leading to serious consequences such as fire, reac-
tor rupture, or environmental contamination. For
example,152 the adiabatic temperature increase at
100% conversion of monomer into polymer is
20
1810 ◦ C for ethylene, 721 ◦ C for acrylonitrile,
542 ◦ C for vinylchloride, and 336 ◦ C for styrene.
In fact, the average heat of polymerization Hp
of a vinylic monomer is about −82 kJ mol−1 , which
is the difference between the sum of the energies
of the two C–C single bonds (∼2 × 346 kJ mol−1 )
formed in the polymer and the bond energy of
a C=C bond (∼610 kJ mol−1 ) of the monomer.
The actual heats of polymerization vary as a result
of secondary effects such as steric strain in the
polymer or differences in the resonance stabiliza-
tion or hydrogen bonding, and solvation between
the monomer and polymer. For example, Hp
varies153 from −35 kJ mol−1 for α-methyl styrene to
−163 kJ mol−1 for tetrafluoroethene (25 ◦ C, liquid
monomer → solid polymer). Detailed discussion of
the thermodynamics of polymerization is provided
in the monograph153 of Sawada. Data on the heats,
entropies, free-energy changes, and ceiling temper-
atures of polymerization of many monomers can be
found there or in the Polymer Handbook .67
3.2 Polymerization Techniques
The different polymerizations according to the
classification on Figure 4 can be carried out
in several ways: bulk polymerization, precipita-
tion polymerization, solution polymerization, slurry
polymerization, gas-phase polymerization, suspen-
sion polymerization, or EP. The polymerization
techniques that are important for industrial RP are
briefly highlighted.
3.2.1 Bulk Polymerization
The only components of a bulk polymerization mix-
ture are monomers, the initiator, and, optionally,
a chain transfer agent. The initiator may be omit-
ted in the case of thermal autoinitiation of styrene.
The main advantage of bulk polymerization is that
a very pure polymer is produced. Furthermore, as
the polymer is not diluted, the volume yield of the
polymer is high. However, the high increase of vis-
cosity during the polymerization makes the stirring
and removal of the heat of polymerization difficult.
A special type of bulk polymerization is precipita-
tion polymerization. Here, the polymer is not soluble
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POLYMERS AND MATERIALS
in its own monomer (e.g., PVC in vinylchloride) and
precipitates during the polymerization. Examples
of polymers prepared by bulk polymerization are
PMMA, general-purpose (or crystalline) PS, and
LDPE.
3.2.2 Solution Polymerization
Solution polymerization is related to bulk polymer-
ization but the components are dissolved in a suit-
able solvent. Both the heat generation and viscosity
of the polymerization mixture are lower because
of dilution. The thermal control of the reactor is
also facilitated because the lower viscosity allows
more efficient cooling. Optionally, cooling can be
achieved by refluxing the solvent. The drawback of
solution polymerization is that the polymer must be
freed from the solvent if it is needed in pure form.
3.2.3 Suspension Polymerization
Suspension polymerization enjoys the advantages of
bulk polymerization but is not plagued with prob-
lems of high viscosity and difficult thermal con-
trol. In this technique, pure monomers containing
the dissolved initiator and, optionally, chain trans-
fer agent are dispersed (suspended) in a continu-
ous water phase (1–1.5 times by mass) in form
of small droplets in the size range of 50–1000 µm.
Both monomer and coreactants must be insoluble in
water. The dispersion of the organic (or oil) phase
in water is effected by stirring in the presence of
added surfactants. Frequently used surfactants are
amphiphilic polymers such as poly(vinyl alcohol),
partially hydrolyzed poly(vinyl acetate), or hydroxy-
propyl methyl cellulose. Micronized inorganic pow-
ders such as CaCO3 , MgCO3 , or Ca3 (PO4 )2 are also
used. The advantage of these inorganic “pickering
dispersants” is that they can be easily removed from
the polymer by treatment with diluted acid. The
droplet size and size distribution are complex func-
tions of the type and concentration of the dispersant,
stirring parameters, reactor, and stirrer geometry, as
well as the physical properties of the dispersed and
continuous phases. From a kinetic point of view,
each droplet behaves as a small bulk polymeriza-
tion reactor. The droplets are transformed during
 RADICAL POLYMERIZATION IN INDUSTRY
the polymerization into rigid spherical polymer par-
ticles which are easily isolated by filtration. The
main advantage of suspension polymerization is the
easy thermal control of the reactor and virtually
constant viscosity of the reaction mass as a whole.
The purity of polymers prepared by this technique
is higher than that obtained in EP and is compa-
rable to that of bulk or solution polymerization.
Examples of polymers made by suspension poly-
merization are PS and PMMA. The most important
production process154 for PVC is suspension poly-
merization of vinylchloride in pressurized (8–12
bar, because of the low boiling point of vinylchlo-
ride) reactors. PVC is not soluble in vinylchloride
and precipitates in the monomer droplets which are
finally transformed into porous polymer particles
(“powder” suspension polymerization).
3.2.4 Emulsion Polymerization
EP, like suspension, mini emulsion, and microemul-
sion polymerization, is a type of heterogeneous
polymerization. It should be noted that hetero-
geneous polymerizations are not only radical in
nature. Heterogeneous polymerizations in aqueous
dispersed media have been reviewed155 by Charleux
and Ganachaud.
EP provides polymer particles of 50–1000 nm dis-
persed in a continuous medium, most often water.
Such polymeric dispersions are called latexes. Syn-
thetic latexes were known already in 1930s but it
was the work during the United States Synthetic
Rubber Program156 (1939–1945) which established
EP as a unique and industrially viable technique. In
the second half of the twentieth century, the method
was further developed and attained a high level
of technical and theoretical understanding. Today,
about 10% of all synthetic polymers or some 20%
of those prepared by RP (>20 × 106 tons per year)
are made by EP.157 The process is named emulsion
polymerization for historical reasons because it was
originally targeted with the polymerization of emul-
sified monomer droplets, and only later it was real-
ized that polymerization occurs not in the monomer
droplets but mainly within the monomer-swollen
latex particles. Among the abundant literature, the
excellent monograph of Herk158 which covers the
history, mechanism, as well as industrial applica-
tions of EP; the books of Asua150,159 ; or the recent
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21
book of Chern160 which additionally treats the
related mini emulsion and microemulsion polymer-
izations can be highlighted. Therefore, only the key
aspects of classical EP will be discussed here. The
simplest EP system consists of a continuous aque-
ous phase, a practically water-insoluble monomer,
a water-soluble initiator, and a colloidal stabilizer
(emulsifier or surfactant). The monomer is dispersed
to form small (0.01–0.1 mm) droplets which are
stabilized against coalescence by a layer of sur-
factant molecules. It is important to note at this
point that “water-insoluble” monomers used in EP
in reality have a very small but measurable solubil-
ity in water: for example, the solubility of styrene
at 50 ◦ C is 4.3 × 10−3 M (see p. 78 of Ref. 158
for the water solubility of industrial monomers).
If the concentration of the surfactant is above the
critical micelle concentration (CMC), the forma-
tion of micelles occurs. These generally spherical
micelles with a diameter of a few nanometers con-
tain ∼102 surfactant molecules and are swollen by
the monomer which migrates from the “reservoir”
droplets through the water phase. The number of
micelles (∼1017 −1019 l−1 ) is many orders of mag-
nitude higher than the number of monomer droplets
(∼1010 l−1 ). Consequently, the surface area of the
micelles is 3–5 orders of magnitude larger than that
of the droplets. The hydrophilic primary radicals
formed in the water phase from the water-soluble
initiator (e.g., ammonium persulfate) do not enter
the lipophilic micelles. They preferentially add to
and propagate with the monomer dissolved in water
until the resulting oligomeric radicals are lipophilic
enough to enter (nucleate) the micelles. Nucleation
of the monomer droplets is insignificant because of
the much larger surface of the micelles compared to
the droplets.
Rapid propagation then follows in the
monomer-swollen micelles leading to latex particles
in a process called heterogeneous nucleation. A
different process called homogeneous nucleation
occurs if the amount of surfactant is below the
CMC. In this case, the oligomeric waterborne
radicals continue to propagate until they became
insoluble enough that they undergo coil-to-globule
transition. The resulting hydrophobic globules are
swollen with monomer and became latex parti-
cles, too. Both heterogeneous and homogeneous
nucleation may be operative in a given system.
Monomer droplets, monomer-swollen micelles, and
monomer-swollen latex particles coexist during the
22
Before polymerization
Monomer
droplet
Figure 6 Emulsion polymerization.
nucleation phase. As the polymerization proceeds,
the number of micelles decreases as they are either
transformed into latex particles or dissociate to
provide surfactant to stabilize the increasing surface
area of the latex particles or globules formed by
homogeneous nucleation. At the end of nucleation
(monomer conversion of 5–10%), all micelles
have disappeared and 1017 –1018 latex particles per
liter are present. They are now the main sites of
polymerization. New monomer diffuses from the
droplets into the latex particles to replace the
monomer consumed there through polymerization.
Consequently, the size of latex particles increases
and that of droplets decreases until they disappear
completely. The polymerization then continues
in the monomer-swollen latex particles until the
monomer is depleted. The result is a polymeric
dispersion in water or a latex (Figure 6).
As the change of viscosity during the course of
EP is very small (similar to suspension process), the
control of the polymerization reactor is simplified.
EP never proceeds to 100% conversion, but leaves
some residual monomer in the waterborne polymer
that must be removed. This can be performed either
via stripping with steam or nitrogen, or through
postpolymerization by addition of fresh initiator.
It is important to note that the basic mechanism
of RP is the same in bulk, suspension, and EP.
However, the distinctive feature of EP is the rad-
ical compartmentalization. In fact, the radicals that
are situated in different particles cannot terminate by
bimolecular termination. Because of the small size
of the latex particles, only one propagating radical
is inside at a given time. Hence, the polymer chain
in the particle grows until a new radical enters and
terminates with the growing one. Therefore, on aver-
age, 50% of particles contain one radical and the rest
none. Nevertheless, due to the enormous number
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POLYMERS AND MATERIALS
After polymerization
Latex particles
Micelles
of particles, the overall radical concentration in the
latex is about one order of magnitude higher than
in a typical bulk polymerization (10−8 M). Conse-
quently, the polymerization rates are higher in EPs
as compared to bulk or suspension process. Radi-
cal compartmentalization also allows longer radical
life times, resulting in polymer chains of a higher
degree of polymerization. The lifetime of the prop-
agating radicals in the particles is inversely propor-
tional to the frequency at which new radicals enter
the particles and terminate with the growing ones.
The entering frequency for a given concentration of
the initiator decreases with the number of particles.
Hence, it is possible to increase the rate of poly-
merization and the molecular weight of the polymer
by simply increasing the number of particles, for
example, by changing the monomer to surfactant
ratio.
The continuous phase in conventional EP is
water. Water-soluble monomers (e.g., acrylamide)
can be polymerized via inverse EP. In this process,
an aqueous solution of the water-soluble monomer
and surfactant is dispersed in an organic phase
(e.g., hexane) and the polymerization is initiated
by lipophilic initiators. The process proceeds via a
mechanism similar to aqueous EP and results in a
dispersion of an aqueous solution of water-soluble
polymer in an organic phase.
About 50% of emulsion polymers are commer-
cialized as waterborne dispersions. It is important
to note that emulsion polymers have in common
the same state of aggregation but are diverse in
chemical composition. A comprehensive overview
of waterborne polymeric dispersions together with
their applications and markets is available in the
monograph11 of Urban and Takamura and of Daniel
and Pichot.12 The main waterborne dispersions and
their respective markets are shown in Table 5.
 RADICAL POLYMERIZATION IN INDUSTRY 23

Table 5 Waterborne polymer dispersions by product class.
• Styrene–butadiene copolymers (paper coatings, paperboard,
carpet backing, adhesives and sealants, additives for mortar
and bitumen), 37%.
• Polyacrylates, polymethacrylates, styrene–acrylate copoly-
mers (paints, coatings, adhesives, inks, paper, and leather
coatings), 30%.
• Vinyl acetate homo- and copolymers (paints, adhesives for
paper and wood), 28%.
solvent resistance, while vinyl chloride improves
fire retardancy and acrylates provide good stabil-
ity against light and heat. An important polymer
property that must be controlled is the glass transi-
tion temperature Tg , which strongly influences the
film formation from a latex and the mechanical
properties of the film. The Tg of a copolymer can
be estimated with the simple Fox equation (11)
or with recently developed161 more sophisticated
models.

A substantial part of emulsion polymers

is commercialized as dry products. Examples
are styrene–butadiene rubber (SBR), acryloni-
trile–butadiene rubber (nitrile rubber), about
75% of ABS copolymer, a small part of PVC,
water-redispersible powders11 for the construction
industry, and polymeric modifiers11 for plastics
(e.g., impact modifiers, processing aids, rheology
modifiers, and so on). Diverse techniques for the
isolation of the polymer from the dispersion are
available: for example, direct spray-drying of the
emulsion or its coagulation followed by drying of
the filter cake.
Standard laboratory formulations for EP contain
water, the monomer, the initiator, and the surfactant.
Commercial recipes are often much more compli-
cated, containing up to 20 components. A large
number of monomers are used in EP either alone
to give homopolymers or, more frequently, as mix-
tures to provide copolymers. In general, random
copolymers are obtained with an inhomogeneous
monomer distribution throughout the chains. Indi-
vidual monomers impart specific properties to the
final polymer. Acrylonitrile, for example, improves
1 WM1 WM2 WMn
= + + ··· + (11)
Tg Tg1 Tg2 Tgn
where Tg refers to the copolymer, Tg1 , Tg2 , . . .
refer to the individual homopolymers, and
WM1 , WM2 , . . . are the weight fractions of
monomers M1, M2, . . . in the copolymer.
In addition to the principal monomers that
make up largest part of the latex (e.g., butadi-
ene, styrene, and so on), small amounts (typi-
cally 2–5% based on the dry polymer) of the
so-called functional monomers are often used. These
important comonomers contain functional groups
(COOH, NH2 , OH) that impart special properties
to both the colloidal system and the polymer. As
EP usually provides polymers of impractically high
molecular weight, chain transfer agents, usually
mercaptans, are often used. Other common addi-
tives include electrolytes (buffers) and metal ion
sequestering agents. A typical list of the compo-
nents of an industrial EP formulation is shown in
Table 6.

Table 6 Components of an industrial emulsion polymerization recipe.

• Monomers (50–55 wt%)

Principal monomers leading to high T g : methyl methacrylate, styrene, acrylonitrile, vinyl chloride, vinyl acetate
Principal monomers leading to low T g : methyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, 1,3-butadiene
Functional monomers: acrylic and methacrylic acid, itaconic acid, fumaric acid, 2-hydroxyethyl acrylate, acrylamide
• Initiators (0.3–0.5 wt%)
Thermal initiators: sodium, potassium or ammonium persulfate, water-soluble azo-compounds
Redox initiators: t-BuOOH or persulfate + Na2 S2 O5
• Surfactants (0.5–3 wt%)
Ionic surfactants: sodium lauryl sulfate, sodium or potassium salts of fatty acids (soaps), salts of alkylbenzene sulfonates
Nonionic surfactants: O-polyoxyethyleneated long-chain alcohols or alkyphenols
• Chain transfer agents: mercaptans
• Sequestering agents: ethylenediamine tetraacetic acid (EDTA) (for complexing of adventitious metal ions, to prevent among other
things their uncontrolled reaction with the redox initiator)
• Electrolytes: alkali metal phosphates (to control the pH)
• Water, sometimes deionized (45%)

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24
3.2.5 Mini- and Microemulsion
Polymerization
The majority of dispersion polymers are prepared
by conventional EP. However, two variants of
classical EP, mini - and microemulsion polymeriza-
tions, are of industrial interest and will, therefore,
be briefly mentioned. A comprehensive discus-
sion of the physicochemical and technological
aspects of mini emulsion polymerization can be
found in the monograph162 of Mittal. The size
of the monomer droplets in a mini emulsion
polymerization160, 162–166 is significantly reduced
(30–500 nm) relative to that in EP (>104 nm).
These small droplets are obtained by intensive
homogenization in the presence of a surfactant
and a small amount of extremely hydrophobic
costabilizer, sometimes called hydrophobe (e.g.,
hexadecane or cetyl alcohol). The hydrophobe
cannot migrate through the aqueous phase and thus
prevents the diffusion of monomer molecules from
smaller droplets to larger ones (Ostwald ripening)
through establishment of counteractive osmotic
pressure in the smaller droplets. As a result, kinet-
ically stable mini emulsions are obtained which
can be polymerized by both water- and oil-soluble
initiators. In contrast to the classical EP, the locus
of polymerization in a mini emulsion is within the
emulsion droplets. The resulting latex can be viewed
as a polymerized copy of the original mini emul-
sion. An important consequence for industry is that
water-insoluble compounds (monomers, polymers,
inorganic solids, pigments, carbon black, additives,
etc.) can be directly incorporated/encapsulated165,166
into the polymer particles by dissolving/dispersing
them in the monomer prior to polymerization. A
practical industrial example is the encapsulation of
light stabilizers167 to render them easily dispersible
in coating formulations. This is not possible via
classical EP since the monomer and the species
dissolved/dispersed in it need to diffuse through the
aqueous phase to the growing polymer particles.
Mini emulsion polymerization bears some similarity
to suspension polymerization. In both cases, the
polymerizing droplet behaves as an individual
batch reactor. The main difference is in the size
and stability of the particles. Ostwald ripening is
much less important in suspension polymerization
because of the very large size of the particles;
hence, addition of hydrophobes is not necessary.
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POLYMERS AND MATERIALS
The monomer droplets are even
smaller (1–30 nm) in microemulsion poly-
merization.160, 168–171 Microemulsions are ther-
modynamically stable, isotropic, transparent, or
translucent systems which are obtained upon
intensive homogenization using a combination of
an anionic surfactant (e.g., sodium dodecyl sulfate)
and a nonionic cosurfactant (e.g., 1-pentanol). This
special surfactant system creates an interfacial
tension at the oil/water interface close to zero.
The high amount of surfactant in microemulsion
formulation leads to a complete surfactant coverage
of the droplets. As in mini emulsion polymerization,
the locus of polymerization is within the emulsion
droplets. The result is very small (∼5–50 nm) poly-
mer particles in coexistence with empty micelles. A
particle contains only a small number of polymeric
chains having a very high molecular weight not
achievable via conventional emulsion or mini emul-
sion polymerization. Potential applications160,171
of microemulsion polymerization include the
synthesis of ultrafine latex particles, water-soluble
polymers with very high molecular weights for
use as flocculants, nanostructured porous materials,
functionalized colloidal particles, and transparent
colloidal systems for photochemical applications.
3.3 Types of Industrial Polymerization
Reactors
Polymer reaction engineering along with the design
of polymerization reactors is a huge discipline
on its own. The excellent book150 of Assua,
the handbook148 of Meyer and Keyrentjes, or
the chapter of Cunningham and Hutchinson in
Ref. 62 is recommended as introductory reading.
Polymerization reactors can be grouped according
to the method by which the reactants are added to
the reaction vessel (Figure 7).
• In a batch reactor, all the reactants are charged
to the reaction vessel at the beginning and no
material is added to or removed from the reactor
during polymerization. After its completion, the
contents are discharged and the reactor is pre-
pared for the next batch. Batch reactors are the
simplest to operate, but offer the least control
over the polymerization. Thus, copolymerization
of monomers with different reactivity ratios or
 RADICAL POLYMERIZATION IN INDUSTRY
Batch Continuous
CSTR
Semibatch Continuous
PFR
Figure 7 Types of reactors commonly used in radical polymer-
ization.
outside the azeotropic monomer feed composition
will result in a broad distribution of copolymer
composition. On the other hand, batch reactors
are readily adaptable to new set of reaction con-
ditions and to new products.
• In a semibatch (or semicontinuous) reactor,
the starting materials can be added, and/or the
products removed, during the polymerization.
Often, only a portion of the total amount of
reactants is initially charged into the reactor.
The polymerization is then started, and more
reactants are added during reaction in order
to control various parameters such as reaction
rate, molecular weight, or copolymer composition
distribution. Any reactant can be fed at a selected,
individual rate.
Semibatch operation is commonly used to
control the copolymer composition distribution.
The compositional drift can be substantially
reduced by maintaining a constant ratio of
monomers in the reactor. Continuous feeding
of initiator and monomers in the desired ratio
helps to control the molecular weight and to
minimize the risk of a thermal runaway reaction
because the monomer concentration remains low
throughout the polymerization (monomer-starved
conditions). Semibatch reactors are widely used
in EP: for example, stainless steel vessels ranging
in size from 20 to 200 m3 and equipped with a
stirrer.
• In a continuous reactor, the reactants are intro-
duced and the products as well as unconsumed
reactants are withdrawn continuously. Continuous
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25
reactor systems include continuous stirred tank
reactors (CSTR), plug flow reactors (PFR), or
combinations of both. The polymerization may
take place in a single reactor or in a cascade of
reactors in which the monomer conversion grad-
ually increases. Continuous reactors are preferred
for large-volume polymers with a limited num-
ber of variations in polymerization conditions.
They offer simplicity of operation, high through-
put rates, uniform product quality, and, hence,
relatively low operating costs.
4 CONTROLLED REVERSIBLE-
DEACTIVATION RADICAL
POLYMERIZATION
A 2010 IUPAC recommendation172 proposes the
term controlled reversible-deactivation radical
polymerization (CRDRP) for polymerizations
previously called controlled radical polymerization
(CRP) or living radical polymerization (LRP).
It was the pioneering discovery173,174 of liv-
ing anionic polymerization by Michael Szwarz
in 1956 that initiated the rapid development of
this field, which has many important applica-
tions in industry. Over the years, other controlled
and living polymerizations such as group-transfer
polymerization, living carbocationic polymerization,
living ring-opening metathesis polymerization, or
living transition-metal-catalyzed alkene polymeriza-
tion were developed. A review of the state of
the art of controlled and living polymerizations in
year 2010 was compiled175 by Müller and Maty-
jaszewski. Its preface also gives clear definitions of
the sometimes controversial terms “controlled” and
“living”.
RP is one of the most important industrial
polymerization techniques. However, prior to the
mid-1990s, classical RP did not allow the synthe-
sis of polymers with precisely designed molecular
architectures such as block, comb, or star copoly-
mers or polymers with defined terminal functional
groups or with predetermined and narrow molecu-
lar weight distributions. This was, however, possible
with the aforementioned nonradical processes. This
situation started to change dramatically with the
seminal work176,177 of Otsu, who in 1982 proposed
a reversible deactivation of the growing chains in
RP using the so-called iniferters.
26 POLYMERS AND MATERIALS

Stable-radical-mediated polymerization, SRMP (NMP) (see Nitroxide-Mediated Polymeriza-

NMP, ORMP; X = Nitroxide, Cobalt complex
k act
Rn
Rn X X
+ (ORMP). The deactivation involves reversible
k deact
kp
Termination
Monomer
Scheme 22 Stable-radical-mediated polymerization.
Today, a plethora of CRP techniques are avail-
able. All are based on reversible deactivation of
growing chains. Most of these chains are in a dor-
mant form and the period of chain growth of an
individual propagating chain may be extended from
∼1 s in conventional RP to a few hours in CRDRP.
At any given instant, only a small fraction of chains
are growing. However, as long as the interconver-
sion of active and dormant forms is rapid compared
to propagation, all chains are able to grow at the
same rate. Therefore, the polymerization takes on
much of the character of a living polymerization.
Nonetheless, it is important to note that, even though
chain termination and irreversible chain transfer are
suppressed to a very low level in such RPs, they are
not completely absent.
CRDRP makes possible the synthesis of block
copolymers by sequential addition of different
monomers. Moreover, if the initiating species are
fully consumed prior to any appreciable chain
growth, all chains grow at the same rate and the
molecular weight distribution of the polymer is
much narrower than in a conventional RP.
Presently, the most important CRDRP techniques
are the following:
• Stable-radical-mediated polymerization (SRMP),
which embraces the nitroxide-mediated RP
tion and its Applications, note, however, that
IUPAC recommends172 the term aminoxyl instead
of nitroxide) and organometallic-mediated RP
coupling with persistent (stable) radicals
(Scheme 22).
• Atom-transfer radical polymerization (ATRP)
(see Atom Transfer Radical Polymeriza-
tion (ATRP) and Addition (ATRA) and
Applications). The deactivation of the radicals
involves reversible atom transfer or reversible
group transfer catalyzed usually, though not
exclusively, by transition-metal complexes
(Scheme 23).
• Degenerate-transfer RP (DTRP) in which
the deactivation of the radicals involves
degenerative transfer of a group (or atom).
Most prominent is the RAFT polymerization
(see Reversible Addition Fragmentation
Chain Transfer (RAFT) Polymerization:
Mechanism, Process and Applications)
(Scheme 24).
A detailed treatment of CRDRP is beyond the
scope of this article and the reader is referred
to recent review articles,178–186 monographs,175
and other articles in this encyclopedia (see
Reversible Addition Fragmentation Chain
Transfer (RAFT) Polymerization: Mechanism,
Process and Applications, Nitroxide-Mediated
Polymerization and its Applications, Atom
Transfer Radical Polymerization (ATRP) and
Addition (ATRA) and Applications, Sb, Bi, Te,
and I-Transfer Polymerization and Applications,
and Fundamentals of Controlled/Living Radical
Polymerization).

Atom-transfer radical polymerization, ATRP

X = Cl, Br; Mt = Cu, Ru, Ni, Fe, Mo...; L = Amines, Phosphines

k act
X Mtn/L Rn X-Mtn+1/L
Rn + +
k deact
kp
Termination
Monomer

Scheme 23 Atom-transfer radical polymerization.

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 RADICAL POLYMERIZATION IN INDUSTRY
Degenerate-transfer radical polymerization, DTRP
X = S-(C = S)Z; RAFT: Z = SR; MADIX: Z = OR
Atom or group transfer: X = I, TeR, SbR2
Rn k tr
+ Rm X k -tr
kp
Monomer
Termination
Scheme 24 Degenerate-transfer radical polymerization.
4.1 Industrial Applications of Controlled
Reversible-Deactivation Radical
Polymerization
CRDRP opens completely new possibilities for the
design and synthesis of novel materials via RP.
As is often the case when revolutionary tech-
nologies emerge, very optimistic forecasts of their
commercial potential appear. Thus, in 2000 the
potential market for CRDRP products was antic-
ipated to exceed 20 billion US$ per year.187
Today, 10 years later, the known industrial appli-
cations of CRDRP are very few. It is now clear
that CRDRP will not replace classical RP for
the production of large-volume commodity poly-
mers. However, its potential for the development
and production of high-value polymeric special-
ties remains intact. Possible target products include
adhesives, binders, compatibilizers, cross-linkers,
dispersants, emulsifiers, leveling agents, lubricants,
sealants, and thermoplastic elastomers. These prod-
ucts are expected to find applications in various
industries such as aerospace, aircraft and automo-
bile, biomedical and cosmetic, coatings, electronics,
home and personal care, and nanotechnology. The
industrial obstacles and achievements of CRDRP
were reviewed187 recently in a very detailed man-
ner by Destarac. Not all CRDRP techniques known
today are equally well suited for upscaling from
small laboratory experiments into large-scale indus-
trial processes. For example, the controlling agent
must be cost effective and ecologically sound. Fur-
thermore, residual metals in ATRP or the chemi-
cal nature of the end groups (RAFT) may be an
issue.
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27
Rm
+ Rn X
kp
Monomer
4.1.1 Nitroxide-Mediated Radical
Polymerization
NMP can be performed using the combination of
a nitroxide radical controller with a conventional
radical initiator such as AIBN or dibenzoylperoxide.
However, the initiator-to-controller ratio is slightly
different for each polymerization system. In fact,
due to the cage reactions of the primary radicals,
excess of the initiator is required to ensure 1 : 1
stoichiometry between the nitroxides and available
primary radicals. For this reason, unimolecular
alkoxyamine initiators such as 56 are preferred
because their homolysis along the relatively weak188
(≈110–140 kJ mol−1 ) NO–R bond affords the
nitroxide and initiating radical in exactly 1:1 ratio
(Scheme 25).
Yet another possibility is the so-called in situ
NMP.189 The required nitroxide radicals are syn-
thesized directly in the polymerizing mixture by
addition of radicals generated from conventional
initiators to nitric oxide, nitroso compounds, or
nitrones, or by the oxidation of suitable secondary
amines or hydroxylamines. This method is of poten-
tial interest for industrial applications because the
nitroxide precursors are cheap. However, a prereq-
uisite for the process optimization is a thorough
understanding of the underlying mechanisms.
It should be noted at this point that
2,2,6,6-tetramethyl-piperidine-N -oxyl (TEMPO)
57 and the related alkoxyamines, for example, 56,
can only be used for controlled polymerization of
styrene and not other monomers such as acrylates.
To overcome this limitation, Ciba (now part of
BASF) has developed a range of proprietary cyclic
nitroxides and unimolecular alkoxyamine initiators
28 POLYMERS AND MATERIALS

kd
N O
N O +
kc

56 57
Unimolecular TEMPO Initiating radical
alkoxyamine initiator

Scheme 25 Unimolecular alkoxyamine initiator.

O O O
O
N O N O NH

N N N
N N N
O O O
O O O
C6H5
C6H5 C6H5
58 59 60 61 62 63

Scheme 26 Sterically hindered cyclic nitroxides and alkoxyamine initiators.

A–B Blockcopolymer
Block A Block B
O O
n m C6H5 O N O
O O
n-Bu-O Me2N n m
Block A
N O O O O
C6H5 120–140 °C 120–140 °C
O Bulk or solution Bulk or solution NMe2
59 64
Stabilizing Anchoring
groups groups

Scheme 27 Amphiphilic block copolymer as pigment dispersant.

that are suitable for controlled polymerization
of both styrene and acrylates. Examples of
these sterically highly hindered piperidine,190
piperazinone,191–193 or diazepanone194 nitroxides
and alkoxyamines 58–62 are shown in Scheme 26.
The piperazinone nitroxide 60 belongs to the
most effective193 cyclic six-membered nitroxides
for NMP known today and its synthesis191,193
is simpler than that195,196 of the equally effec-
tive195 tetraethyl-piperidone-N -oxyl 63. The indus-
trial NMP process was reported197 by Ciba in
2003. Using NMP, Ciba developed and com-
mercialized a range of block copolymer pigment
dispersants197–203 which offer advantages in rhe-
ology of pigment concentrates, their stability, and
coloring properties. The optimal block copolymer
pigment dispersant consists of (i) a B-block bearing
suitable anchoring groups (e.g., dialkylamino),
which adsorb to the surface of a pigment particle;
and (ii) an A-block with stabilizing groups which
compatibilize the dispersant within the medium
and prevent pigment agglomeration and coagula-
tion. The design and synthesis of the amphiphilic
blockcopolymer 64 by NMP using the alkoxyamine
initiator 59 is exemplified in Scheme 27. The chem-
istry and physics of polymeric pigment dispersants
have been reviewed202 by Auschra and Pirrung.
In 2005, Elf Atochem (now Arkema) com-
mercialized SG-1 (65), an acyclic phosphonylated
α-hydrido nitroxide204,205 and BlocBuilder MA206
(66), its related alkoxyamine206–208 which allows
controlled polymerization of styrenic, acrylic, and
some acrylamido monomers (Scheme 28).

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 RADICAL POLYMERIZATION IN INDUSTRY
O
O N
N P OEt
N P OEt
O OEt
O OEt
COOH
65 SG-1 66 Blocbuilder®
Scheme 28 Acyclic and indolyl nitroxides and alkoxyamines.
Recently, Arkema reported the development209
of NMP-based block copolymers (Nanostrength)
consisting of PMMA surrounding a center block
of poly(butyl acrylate). However, only the central
poly(butyl acrylate) block is controlled. These
copolymers can be used as tough thermoplastics,
thermoplastic elastomers, or toughening additives
for epoxy thermosets. NMP is not suitable for
polymerization of nonconjugated monomers such as
vinyl acetate, vinyl chloride, or N -vinyl pyrrolidone.
Also unsolved is the controlled homopolymeriza-
tion of methacrylates although promising results
were reported210 with the indolyl nitroxide 68.
However, well-controlled and living copolymer-
ization of methyl methacrylate with only 5–10%
of styrene211 or acrylonitrile212 or as little 1%
of 9-(4-vinylbenzyl)-9-H -carbazole213 is possible.
From the industrial point of view, it is important that
NMP, ATRP, and RAFT are amenable155, 214–220 to
aqueous emulsion or mini emulsion polymerization
even though some issues221 remain to be solved.
One issue is that NMP requires relatively high
temperatures, typically in the range of 100–140 ◦ C.
Interesting attempts have been made to use nitroxide
mediators in radical photopolymerization.222
A low-cost and upscalable synthesis of nitroxides
or the related alkoxyamines is necessary to allow
their use in industrial NMP. For example, the
relatively expensive TEMPO 57 can be replaced
by the much cheaper and industrially available 4-
hydroxy-2,2,6,6-tetramethyl-piperidine-N -oxyl or
its readily available 4-alkoxy- or 4-acyloxy
derivatives for polymerization of styrene. The
nitroxides 58,190,194 60,191,193 and 65223,224
can be prepared by simple reactions with-
out expensive organometallic reagents, as
is the case for the TIPNO225 (N -tert-butyl-
N -2-methyl-1-phenylpropyl nitroxide) nitroxide 67
which is very popular in academic laboratories.
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N
O N
O
67 TIPNO 68
Similarly, transformation of the nitroxide into the
corresponding alkoxyamine initiator (e.g., 58 to 59
or 65 to 66) must be industrially feasible. A variety
of methods for the preparation of alkoxyamimes
exist,226–229 but only a few are suitable for
large-scale, multiton synthesis. The reported
industrially relevant methods rely on coupling of
nitroxides with C-centered radicals, which, in turn,
are generated from either activated alkyl halides
with Cu or Cu(I) salts230 or from hydrocarbons
and t-butylhydroperoxide.231 In most cases, the
nitroxide group remains covalently attached to the
NMP polymer. This is usually not a problem, but,
nevertheless, possibilities232 for its removal exist.
4.1.2 Atom-Transfer Radical Polymerization
ATRP is arguably among the most versatile CRDRP
method for building complex polymer architec-
tures with a high degree of precision. It can be
run over a large range of temperatures, starting at
0 ◦ C or below, with a broad range of monomers
(with the exception of acids) using relatively eas-
ily accessible (optionally functionalized) initiators.
Despite this, the method was not readily accepted
by industry because of the large amounts of metal-
lic catalysts (0.1–1 mol% vs monomer) and lig-
ands required. Even though several methods for
catalyst removal233 exist, they are too expensive
on an industrial scale. Significant progress was
made possible with the invention of activators
regenerated by electron transfer (ARGET)181, 234–236
and initiators for continuous activator regenera-
tion (ICAR)181,237 modifications of ATRP by Maty-
jaszewski and coworkers. In ARGET–ATRP, an
excess of reducing agent (e.g., ascorbic acid, cop-
per(0), or tin octoate) relative to catalyst is used to
continuously regenerate the Cu(I) activator species
30
COOR
Br
69
N
N N
N N
N N
72
PMDETA
Scheme 29 Alkyl halides and ligands for ATRP.
by reduction of Cu(II) products which are formed
by unavoidable radical termination. In ICAR–ATRP
polymerization, radicals are continuously generated
by conventional initiators (e.g., AIBN) to reduce the
Cu(II) species and thus regenerate the active Cu(I)
activators. Using these techniques, the amount of
Cu catalyst can be reduced238 by several orders of
magnitude down to 10–50 ppm. This low amount
of residual Cu catalyst may be acceptable for some
applications. Use of ARGET to reduce the con-
centration of the Cu catalyst in solution–ATRP in
batch, semibatch, and continuous reactors has been
reviewed.239
A new dimension in the reduction of Cu
catalyst in ATRP is represented by the single-
electron-transfer-controlled radical polymerization
(SET-CRP) developed by Percec et al .240–243 In
this method, Cu(0) activates the polymerization and
is converted by transfer of an electron to the alkyl
halide (initiator or dormant chain) into a Cu(I)
species. The latter rapidly disproportionates in polar
solvents (H2 O, alcohols, dipolar aprotic solvents)
in the presence of amine ligands into Cu(0) and
the Cu(II) deactivator. The atomic Cu(0) catalyst
is much more reactive than the Cu(I) species used
in ATRP, so that only small amounts have to
be used. SET-CRP allows rapid polymerization
of both activated (acrylates, methacrylates) and
nonactivated (vinyl chloride) monomers in envi-
ronmentally friendly solvents at room temperature
with even less catalysts than ARGET or ICAR. It
is expected that these new advances will facilitate
implementation of ATRP in industry, which up
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POLYMERS AND MATERIALS
Br COOR
Br
70 71
N N
N N
N
N N
N
73 74 75
Ligand activity
to now, similarly to other CRDRP techniques,
has not proceeded as fast as originally expected.
Matyjaszewski at Carnegie Mellon University
founded the ATRP Consortium (1996–2001)
and the CRP Consortium (2001–present)244 with
the goal to assist major industrial companies
in this transfer. One success was registered
by Kaneka, which commercialized180,187 mois-
ture and photocurable telechelic polyacrylates
prepared by ATRP for use as sealants and adhe-
sives, or in coatings. In addition, at least two
start-up companies, “ATRP Solutions,”245 and
“Warwick Effect Polymers,”187,246 are foster-
ing industrial ATRP. Finally, the availability of
the ATRP reagents deserves a brief comment.
Copper and Cu(I) salts as well as the typi-
cally used alkyl halides, for example, 69–71
(Scheme 29), are readily available. The situation
is more complicated with the amine ligands. Only
N, N, N , N , N  -pentamethyl-diethylenetriamine
(PMDETA) 72 is commercially available (e.g.,
BASF) in large quantities but not the most
effective235 ligands, for example, 73–75.
4.1.3 Degenerate-Transfer Radical
Polymerization
By far the most important method of DTRP is
RAFT, which is an extremely versatile tool for
the synthesis of complex polymeric architectures
in bulk, organic, or water solution or in dispersed
media. It is compatible with the widest range of
 RADICAL POLYMERIZATION IN INDUSTRY
S S
S S
N
76
Dithioester Dithiocarbamate
Scheme 30 Examples of RAFT/MADIX agents.
polymerizable monomers of all CRDRP techniques.
From the process point of view, a RAFT agent
can simply replace the conventional chain transfer
agent, requiring little or no change in established
industrial setups. This broad applicability puts247
RAFT in the position to become a key industrial
CRP method. All aspects of RAFT are covered in
the “Handbook of RAFT Polymerization”248 and in
recent reviews.209,247,249–251
Similar to alkoxyamines in NMP, RAFT agents
must be readily available. A recent overview252
covers various RAFT agents and their synthesis.
Scheme 30 shows examples 76–79 of typical
RAFT agents. Note that RAFT using xanthates as
controlling agents is called macromolecular design
by interchange of xanthates (MADIX).253
The trithiocarbonate 78 (BlocBuilder DB)206
was developed by Arkema to commercial stage, and
the xanthate 79 (Rhodixan A1) can be obtained
under licence from Rhodia. However, RAFT poly-
mers are always yellow to red in color, which
is clearly not acceptable in many applications.
Fortunately, a variety of methods251,254 are avail-
able to remove the thiocarbonylthio end group
from the polymer or use it for further trans-
formations, for example, for synthesis of block
copolymers. Advances in synthesis of degradable
“green” polymer materials via RAFT have been
reviewed255 by Perrier and Semsarilar. Rhodia
recently reported256,257 the use of MADIX for the
development and commercialization of Rhodibloc
RS block copolymers for the stabilization of
emulsions.
Last but not least, it should be mentioned
that the first industrially applied CRP was most
likely the iodine-transfer polymerization258 used by
Daikin Industries for the preparation of fluorinated
thermoplastic elastomers.187
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31
COOCH3
S S
S S
S O
77 78 79
Trithiocarbonate Xanthate (MADIX agent)
5 MAIN COMMERCIAL POLYMERS MADE BY
RADICAL POLYMERIZATION
It is beyond the scope of this article to discuss
the synthesis and properties of the individual poly-
mers that are made by RP. A detailed overview
appears, for example, in the “Industrial Polymers
Handbook ”17 or the book18 by Campo. The mono-
graph259 of Scheirs and Priddy provides in-depth
information on all aspects of styrenic polymers and
copolymers. Excellent monographs11,12 on disper-
sion polymers are also available. Abundant informa-
tion on PVC can be found in the “Practical Guide
to Polyvinyl Chloride”260 and in the special issue
(2002, vol. 27(10)) of Progress in Polymer Science.
The technical processes of PVC production have
been reviewed154 by Saeki and Emura. Development
of PVC from its discovery to mass production is
recounted by Braun.261 Comprehensive information
on polyethylenes, including LDPE which is made
by RP, is available in “Practical Guide to Polyethy-
lene”262 or in Ref. 121.
6 CONCLUSION
Conventional RP has reached a very high level
of sophistication and is among the most important
industrial polymerization techniques; about 45% of
all synthetic polymers are made via this method. The
most rapidly developing area of synthetic polymer
chemistry today is CRP. Even though considerable
progress has been made in CRP during the last two
decades, only a very small part of its tremendous
potential could be put into industrial practice up to
now. However, the recent advances in CRP give
reason to expect that new, high-valued products,
rather than replacements for existing polymers, will
be developed in the very near future.
32 POLYMERS AND MATERIALS
REFERENCES
1. S. Penczek and G. Moad, Pure Appl. Chem., 2008, 80,
2163–2193.
2. H.-G. Elias, Macromolecules, Wiley-VCH Verlag GmbH,
Weinheim, 2005, vol. 1.
3. R. Olby, J. Chem. Educ., 1970, 47, 168–174.
4. H. Morawetz, Polymers: The Origin and Growth of a
Science, John Wiley & Sons, Inc, New York, 1985.
5. PlacticsEurope, Plastics— the Facts 2010, http://www.
plasticseurope.org/plastics-industry/market- data.aspx.
(accessed 14 July 2011).
6. L. Bewley, G. D. Morris, and N. Alperowicz, Plastics.
Chem. Week , 2010. October 18th.
7. J.-P. Pascault, H. Sautereau, J. Verdu, and R. J. J. Williams,
Thermosetting Polymers, Marcel Dekker, New York,
2002.
8. S. H. Goodman, Handbook of Thermoset Plastics, Noyes
Publications, New Jersey, 1998.
9. W. F. Gum, W. Riese, and H. Ulrich, eds., Reaction
Polymers: Polyurethanes, Epoxies, Unsaturated Polyesters,
Phenolics, Special Monomers, and Additives. Chemistry,
Technology, Applications, Markets, Hanser Publishers,
Muenchen, 1992.
10. R. G. Jones, W. Ando, and J. Chojnowski, eds., Silicon
Containing Polymers, Kluwer Academic Publishers, Dor-
drecht, 2000.
11. D. Urban and K. Takamura, eds., Polymer Dispersions and
their Industrial Applications, Wiley-VCH Verlag GmbH,
Weinheim, 2002.
12. J.-C. Daniel and C. Pichot, eds., Les Latex Synthétiques:
Élaboration— Propriétés— Applications, Lavoisier, Paris,
2006.
13. M. McCoy, M. S. Reisch, and et al ., A. H. Tullo, Facts
and Figures of the Chemical Industry, Chem. Eng. News,
2010, 88, 54–62.
14. H. Dominighaus, P. Elsner, P. Eyerer, and T. Hirth,
Kunststoffe: Eigenschaften und Anwendungen, 7th edn,
Auflage, Springer-Verlag, Berlin Heidelberg, 2008.
15. Kunststoff-Information, Polymerpreise, http://www.
kiweb.de/. (accessed 14 July 2011).
16. Fachinformationszentrum Chemie, ed., Index of Polymer
Trade Names, Wiley-VCH Verlag GmbH, Weinheim,
1992.
17. E. S. Wilks, ed., Industrial Polymers Handbook ,
Wiley-VCH Verlag GmbH, Weinheim, 2001.
18. E. A. Campo, Industrial Polymers, Carl Hanser Verlag,
Munich, 2008.
19. M. Chanda and S. K. Roy, Industrial Polymers, Specialty
Polymers and Their Applications, CRC Press, Boca Raton,
FL, 2009.
20. F. Mohammad, Specialty Polymers: Materials and Appli-
cations, Anshan, Kent, 2007.
21. J. A. Brydson, Plastic Materials, 7th ed,
Butterworth-Heinemann, Oxford, 1999.
22. G. Franz, Oxidation, Ullmann’s Encyclopedia of Industrial
Chemistry, 6th edn, Wiley-VCH Verlag GmbH, Weinheim,
2003.
23. H. S. Mark, ed., Encyclopedia of Polymer Science and
Technology, 3rd edn, John Wiley & Sons, Inc, New York,
2004.
Encyclopedia of Radicals in Chemistry, Biology and Materials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Radicals in Chemistry, Biology and Materials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470971253.rad080
24. Kirk-Othmer Encyclopedia of Chemical Technology, 5th
edn, John Wiley & Sons, Inc, New York, 2007.
25. H. L. Hsieh and R. P. Quirk, Anionic Polymerization:
Principles and Practical Applications, Marcel Dekker,
New York, 1996.
26. K. Matyjaszewski, ed., Cationic Polymerizations: Mech-
anisms, Synthesis & Applications, Marcel Dekker, New
York, 1996.
27. R. Faust and T. D. Shaffer, eds., Cationic Polymerization:
Fundamentals and Applications, ACS Symposium Series,
American Chemical Society, Washington, DC, 1997,
vol. 665.
28. H. L. Hsieh, Industrial applications of anionic polymer-
ization: an introduction, Applications of Anionic Poly-
merization Research, ACS Symposium Series, American-
break Chemical Society, Washington, DC, 1998, vol. 696,
pp. 28–33.
29. K. Matyjaszewski, Y. Gnanou, and L. Leibler, eds.,
Macromolecular Engineering, Wiley-VCH Verlag GmbH,
Weinheim, 2007, vol. 1.
30. M. E. Rogers and T. E. Long, eds., Synthetic Methods in
Step-growth Polymers, John Wiley & Sons, Inc, Hoboken,
NJ, 2003.
31. K. G. Johnson and L. S. Yang, Preparation, properties
and applications of unsaturated polyesters, in Modern
Polyesters, eds. J. Scheirs and T. E. Long, John Wiley
& Sons, Inc, Hoboken, NJ, 2003, pp. 699–713.
32. K. J. Ivin and J. C. Mol, Olefin Metathesis and Metathesis
Polymerization, Academic Press, San Diego, CA, 1997.
33. W. Kuran, Principles of Coordination Polymerisation,
John Wiley & Sons, Ltd, Chichester, 2001.
34. B. Rieger, L. S. Baugh, S. Kacker, and S. Striegler,
eds., Late Transition Metals Polymerization Catalysis,
Wiley-VCH Verlag GmbH, Weinheim, 2003.
35. Y. V. Kissin, Alkene Polymerization Reactions with Tran-
sition Metal Catalysts, Elsevier, Amsterdam, 2008.
36. R. Hoff and R. T. Mathers, eds., Handbook of Transition
Metals Polymerization Catalysts, John Wiley & Sons, Inc,
Hoboken, NJ, 2010.
37. O. W. Webster, J. Polym. Sci., Part A: Polym. Chem., 2000,
38, 2855–2860.
38. H. J. Lanson, Chemistry and technology of alkyd and satu-
rated reactive polyester resins, ACS Symposium Series,
American Chemical Society, Washington, DC, 1985,
vol. 285, pp. 1181–1204.
39. J. W. Gooch, Emulsification and Polymerization of
Alkyd Resins, Kluwer Academic Publishers, New York,
2002.
40. Z. W. Wicks, Alkyd resins, Kirk-Othmer Encyclopedia of
Chemical Technology, 5th edn, John Wiley & Sons, Inc,
Hoboken, NJ, 2004, vol. 2, p 147–169.
41. J. Jagur-Grodzinski, Prog. Polym. Sci., 1992, 17, 361–415.
42. B. I. Chaudhary, S. S. Sengupta, J. M. Cogen, and
M. Curto, Polym. Eng. Sci., 2011, 51, 237–246.
43. C. Tzoganakis, J. Vlachopoulos, and A. E. Hamielec,
Polym. Eng. Sci., 1988, 28, 170–180.
44. A. Psarreas, C. Tzoganakis, N. McManus, and A. Penlidis,
Polym. Eng. Sci., 2007, 47, 2118–2123.
45. H. Guangjian and C. Tzoganakis, Polym. Eng. Sci., 2011,
51, 151–157.
46. G. Moad, Prog. Polym. Sci., 1999, 24, 81–142.
 RADICAL POLYMERIZATION IN INDUSTRY
47. E. P. Collar and J. M. Garcia-Martinez, On chemical
modified polyolefins by grafting of polar monomers: a
survey based on recent patents literature, Recent Patents
on Materials Science, Bentham Science Publishers, 2010,
vol. 3, pp. 76–91.
48. E. Passaglia, S. Coiai, and S. Augier, Prog. Polym. Sci.,
2009, 34, 911–947.
49. G. Scott, ed., Mechanism of Polymer Degradation and
Stabilisation, Elsevier, London, 1990.
50. N. S. Allen and M. Edge, Fundamentals of Polymer
Degradation and Stabilisation, Elsevier, Barking, 1992.
51. H. Zweifel, Stabilization of Polymeric Materials, Springer,
Berlin, Heidelberg, 1998.
52. H. Zweifel, ed., Plastic Additives Handbook , Hanser
Publishers, Munich, 2001.
53. J. Scheirs and D. Priddy, eds., Modern Styrenic Polymers,
John Wiley & Sons, Ltd, Chichester, 2003, p. 557.
54. G. Moad and D. Solomon, The Chemistry of Radical
Polymerization, 2nd edn, Elsevier, Oxford, 2006.
55. K. O. Havelka and C. L. McCormick, eds., Specialty
Monomers and Polymers: Synthesis, Properties, and Appli-
cations, ACS Symposium Series, American Chemical
Society, Washington, DC, 2000, vol. 755.
56. G. Webster, G. Bradley, and C. Lowe, A Compilation of
Oligomers & Monomers Commercially Available for UV
Today, Sita Technology, Edinbourgh, 2001.
57. H.-J. Arpe, Industrial Organic Chemistry, 5th edn,
Wiley-VCH Verlag GmbH, Weinheim, 2010.
58. F. Sasse and G. Emig, Chem. Eng. Technol., 1998, 21,
777–789.
59. R. Diercks, J. D. Arndt, S. Freyer, et al ., Chem. Eng.
Technol., 2008, 31, 631–637.
60. M. N. Belgacem and A. Gandini, eds., Monomers,
Polymers and Composites from Renewable Resources,
Elsevier, Oxford, 2008.
61. J.-F. Lutz, Polym. Chem., 2010, 1, 55–62.
62. K. Matyjaszewski and T. P. Davis, eds., Handbook
of Radical Polymerization, John Wiley & Sons, Inc,
Hoboken, NJ, 2002.
63. M. Buback and A. M. Herk, eds., Radical Polymerization:
Kinetics and Mechanism, Wiley-VCH Verlag GmbH,
Weinheim, 2007.
64. K. Matyjaszewski and W. A. Braunecker, Radical
polymerization, in Macromolecular Engineering, eds.
K. Matyjaszewski, Y. Gnanou, and L. Leibler, Wiley-VCH
Verlag GmbH, Weinheim 2007, vol. 1, pp. 161–215.
65. G. Odian, Principles of Polymerization, 3rd edn, John
Wiley & Sons, Inc, New York, 1991.
66. E. T. Denisov, T. G. Denisova, and T. S. Pokidova,
Handbook of Free Radical Initiators, John Wiley & Sons,
Inc, Hoboken, NJ, 2003.
67. J. Brandup, E. H. Immergut, and E. A. Grulke, eds.,
Polymer Handbook , 4th edn, John Wiley & Sons, Inc, New
York, 1999.
68. D. Braun, Int. J. Polym. Sci., 2009. Article ID 893234
http://www.hindawi.com/journals/ijps/2009/893234.html.
(accessed 14 July 2011).
69. H. K. Hall, Angew. Chem., Int. Ed. Engl., 1983, 22,
440–455.
70. G. Clouet, P. Chaumont, and P. Corpart, J. Polym. Sci.,
Part A: Polym. Chem., 1993, 31, 2815–2824.
71. P. S. Engel, Chem. Rev., 1980, 80, 99–150.
Encyclopedia of Radicals in Chemistry, Biology and Materials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Radicals in Chemistry, Biology and Materials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470971253.rad080
33
72. G. Ayrey, Chem. Rev., 1963, 63, 645–667.
73. H. Ishiwata, T. Inoue, and K. Yoshihira, J. Chromatogr.,
1986, 370, 275–279.
74. P. J. Fordham, J. W. Gramshaw, and L. Castle, Food Addit.
Contam., 2001, 18, 461–471.
75. J. Krstina, G. Moad, R. Ian Willing, et al ., Eur. Polym. J.,
1993, 29, 379–388.
76. J. Krstina, G. Moad, and D. H. Solomon, Eur. Polym. J.,
1989, 25, 767–777.
77. Wako Pure Chemical Industries, Azoinitiators, http://
www.wako-chem.co.jp/specialty/index.htm. (accessed 14
July 2011).
78. Plastics Additives 7. A global study, Organic Peroxides,
Townsend Polymer Services and Information, Houston,
2007, Chapter 15.
79. Z. Rappoport, ed., The Chemistry of Peroxides, John Wiley
& Sons, Ltd, Chichester, 2006, vol. 2, Parts 1–2.
80. Y. R. Luo, Comprehensive Handbook of Chemical Bond
Energies, CRC Press, Boca Raton, FL, 2007.
81. W. H. Starnes, Prog. Polym. Sci., 2002, 27, 2133–2170.
82. S. Srinivas and K. G. Taylor, J. Org. Chem., 1990, 55,
1779–1786.
83. P. F. Bruins, ed., Unsaturated Polyester Technology,
Gordon and Breach, New York, 1976.
84. J. R. Ebdon, T. N. Huckerby, and T. C. Hunter, Polymer,
1994, 35, 250–256.
85. G. S. Misra and U. D. N. Bajpai, Progr. Polym. Sci., 1982,
8, 61–131.
86. J. A. Klein and G. R. Mros, Process Saf. Prog., 2006, 25,
303–310.
87. Arkema, Organic Peroxides Safety,
http://www.arkema-inc.com/index.cfm?pag=320.
(accessed 14 July 2011).
88. K. Studer, P. Nesvadba, T. Jung, et al ., Prog. Org. Coat.,
2008, 61, 119–125.
89. M. Roth, R. Pfaendner, P. Nesvadba, and M.-O. Zink,
WO2001/090113 A1, Ciba SC, 2001.
90. E. De Leon-Saenz, G. Morales, R. Guerrero-Santos, and
Y. Gnanou, Macromol. Chem. Phys., 2000, 201, 74–83.
91. P. Nesvadba, L. Bugnon, and T. Wagner, Chimia, 2010,
64, 56–58.
92. J. V. Crivello and K. Dietliker, Photoinitiators for Free
Radical Cationic and Anionic Photopolymerization, John
Wiley & Sons in association with SITA Technology,
Chichester, 1998.
93. K. Dietliker, A Compilation of Photoinitiators Commer-
cially Available for UV Today, Sita Technology, Edinburgh,
2002.
94. H. F. Gruber, Prog. Polym. Sci., 1992, 17, 953–1044.
95. K. Dietliker, R. Hüsler, J. L. Birbaum, et al ., Prog. Org.
Coat., 2007, 58, 146–157.
96. J. P. Fouassier, X. Allonas, and J. Lalevée, Polymerization
under light and other external stimuli, in Macromolecular
Engineering, eds. K. Matyjaszewski, Y. Gnanou, and
L. Leibler, Wiley-VCH Verlag GmbH, Weinheim 2007,
vol. 1, pp. 643–672.
97. C. Lowe, G. Webster, S. Kessel, and I. McDonald,
Chemistry and Technology for UV and EB Formulation
for Coatings, Inks and Paints, John Wiley & Sons in
association with SITA Technology, Chichester, 1997.
34 POLYMERS AND MATERIALS
98. R. Mehnert, A. Pincus, I. Janorski, and R. Stove, UV & EB
Curing Technology and Equipment, John Wiley & Sons in
association with SITA Technology, Chichester, 1998.
99. J.-P. Fouassier and J. F. Rabek, eds., Radiation Curing
in Polymer Science and Technology: Fundamentals and
Methods, Elsevier, London, 1993, vol. 1.
100. J.-P. Fouassier and J. F. Rabek, eds., Radiation Curing in
Polymer Science and Technology: Photoinitiating Systems,
Elsevier, London, 1993, vol. 2.
101. J.-P. Fouassier and J. F. Rabek, eds., Radiation Curing in
Polymer Science and Technology: Polymerization Mecha-
nisms, Elsevier, London, 1993, vol. 3.
102. J.-P. Fouassier and J. F. Rabek, eds., Radiation Curing
in Polymer Science and Technology: Practical Aspects and
Applications, Elsevier, London, 1993, vol. 4.
103. A. R. Marrion, ed., The Chemistry and Physics of Coatings,
2nd edn, The Royal Society of Chemistry, Cambridge,
2004.
104. U. Fink, F. Hajduk, Y. Wei, and Y. Ishikawa, Radiation
Curable Coatings, SRI Consulting, 2008.
105. H. Kura, J. Tanabe, H. Oka, et al ., New Oxime Ester
Photoinitiators for Color Filter Resists, RadTech Report,
RadTech International North America, 2004, vol. 18 (3),
pp. 30–35.
106. K. Dietliker, T. Jung, J. Benkhoff, et al ., Macromol. Symp.,
2004, 217, 77–97.
107. A. G. Merzlikine, S. V. Voskresensky, E. O. Danilov,
et al ., Photochem. Photobiol. Sci., 2007, 6, 608–613.
108. A. Matsumoto, M. Kikuta, and M. Oiwa, J. Polym. Sci.,
Polym. Lett. Ed., 1986, 24, 7–11.
109. G. Moad, E. Rizzardo, and D. H. Solomon, Macro-
molecules, 1982, 15, 909–914.
110. G. Moad, D. H. Solomon, S. R. Johns, and R. I. Willing,
Macromolecules, 1982, 15, 1188–1191.
111. O. Vogl, M. F. Qin, and A. Zilkha, Prog. Polym. Sci., 1999,
24, 1481–1525.
112. N. Moszner and U. Salz, Prog. Polym. Sci., 2001, 26,
535–576.
113. N. Moszner, T. Volkel, and V. Rheinberger, Macromol.
Chem. Phys., 1997, 198, 749–762.
114. F. R. Mayo and F. M. Lewis, J. Am. Chem. Soc., 1944, 66,
1594–1601.
115. T. Alfrey and C. C. Price, J. Polym. Sci., 1947, 2, 101–106.
116. G. C. Laurier, K. F. O’Driscoll, and P. M. Reilly, J. Polym.
Sci., Polym. Symp., 1985, 72, 17–26.
117. G. Moad, D. H. Solomon, T. H. Spurling, and D. J. Vearing,
Aust. J. Chem., 1986, 39, 1877–1881.
118. F. Quella, Makromol. Chem., 1989, 190, 1445–1452.
119. J. Chiefari and E. Rizzardo, Control of free radical
polymerization by chain transfer methods, in Hand-
book of Radical Polymerization, eds. T. P. Davis and
K. Matyjaszewski, John Wiley & Sons, Inc, Hoboken, NJ,
2002, pp. 629–690.
120. T. Corner, Adv. Polym. Sci., 1984, 62, 95–142.
121. K. S. Whiteley, Polyethylene, in Industrial Polymers
Handbook , ed. E. S. Wilks, Wiley-VCH Verlag GmbH,
Weinheim, 2001, vol. 2, p. 643–691.
122. F. R. Mayo, J. Am. Chem. Soc., 1943, 65, 2324–2329.
123. R. G. W. Norrish and R. R. Smith, Nature, 1942, 150,
336–337.
124. V. E. Trommsdorff, H. Köhle, and P. Lagally, Makromol.
Chem., 1948, 1, 169–198.
Encyclopedia of Radicals in Chemistry, Biology and Materials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Radicals in Chemistry, Biology and Materials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470971253.rad080
125. Arkema. Mercaptans, http://www.arkema-inc.com/index.
cfm?pag=123. (accessed 14 July 2011).
126. Chevron Phillips Chemical, Mercaptans, http://www.
cpchem.com/bl/specchem/en-us/Pages/Mercaptans.aspx.
(accessed 14 July 2011).
127. B. Boutevin, J.-M. Lusinchi, Y. Pietrasanta, and
J.-J. Robin, Eur. Polym. J., 1994, 30, 615–619.
128. F. A. Bovey and I. M. Kolthoff, Chem. Rev., 1948, 42,
491–525.
129. F. Tüdos and T. Földes-Berezsnich, Prog. Polym. Sci.,
1989, 14, 717–761.
130. S. Ilg, E. Pighetti, P. Nesvadba, and A. Fuchs, WO
2006/111494 A1, CibaSC, 2006.
131. J. J. Kurland, J. Polym. Sci., Polym. Chem. Ed., 1980, 18,
1139–1145.
132. L. B. Levy, J. Polym. Sci., Polym. Chem. Ed., 1985, 23,
1505–1515.
133. L. B. Levy and J. D. Penrod, Plant/Oper. Prog., 1989, 8,
105–108.
134. S. Schulze and H. Vogel, Chem. Eng. Technol., 1998, 21,
829–837.
135. B. Maillard, K. U. Ingold, and J. C. Scaiano, J. Am. Chem.
Soc., 1983, 105, 5095–5099.
136. L. Gou, C. N. Coretsopoulos, and A. B. Scranton, J. Polym.
Sci., Part A: Polym. Chem., 2004, 42, 1285–1292.
137. P. Neta, R. E. Huie, and A. B. Ross, J. Phys. Chem. Ref.
Data, 1990, 19, 413–513.
138. K. U. Ingold, Acc. Chem. Res., 1969, 2, 1–9.
139. V. A. Bhanu and K. Kishore, Chem. Rev., 1991, 91,
99–117.
140. L. Gou, B. Opheim, and A. B. Scranton, Methods to
overcome oxygen inhibition in free radical photopolymer-
izations, in Photochem. UV Curing, ed. J. P. Fouassier,
Research Signpost, Trivandrum, 2006, pp. 301–310.
141. C. Belon, X. Allonas, C. Croutxe-barghorn, and J. Lalevee,
J. Polym. Sci., Part A: Polym. Chem., 2010, 48,
2462–2469.
142. M. Höfer, N. Moszner, and R. Liska, J. Polym. Sci., Part
A: Polym. Chem., 2008, 46, 6916–6927.
143. L. Feng and B. I. Suh, J. Appl. Polym. Sci., 2009, 112,
1565–1571.
144. R. Shenoy and C. N. Bowman, Macromolecules, 2010, 43,
7964–7970.
145. C. E. Hoyle and C. N. Bowman, Angew. Chem. Int. Ed.,
2010, 49, 1540–1573.
146. M. J. Kade, D. J. Burke, and C. J. Hawker, J. Polym. Sci.,
Part A: Polym. Chem., 2010, 48, 743–750.
147. A. B. Lowe, Polym. Chem., 2010, 1, 17–36.
148. T. Meyer and J. Keurentjes, eds., Handbook of Polymer
Reaction Engineering, Wiley-VCH Verlag GmbH, Wein-
heim, 2005.
149. W. Keim, Kunststoffe. Synthese, Herstellungsverfahren,
Apparaturen, Wiley-VCH Verlag GmbH, Weinheim,
2006.
150. J. M. Asua, ed., Polymer Reaction Engineering, Blackwell
Publishing, Oxford, 2007.
151. D. H. Sebastian and J. A. Biesenberger, Polym. Eng. Sci.,
1979, 19, 190–197.
152. U. Onken and A. Behr, Chemische Prozesskunde, Band 3 ,
Georg Thieme Verlag, Stuttgart, 1996, p. 81.
153. H. Sawada, Thermodynamics of Polymerization, Marcel
Dekker, New York, 1976.
 RADICAL POLYMERIZATION IN INDUSTRY
154. Y. Saeki and T. Emura, Prog. Polym. Sci., 2002, 27,
2055–2131.
155. B. Charleux and F. Ganachoud, Polymerizations in aqueous
dispersed media, in Macromolecular Engineering, eds.
K. Matyjaszewski, Y. Gnanou, and L. Leibler, Wiley-VCH
Verlag GmbH, Weinheim, 2007, vol. 1, pp. 605–642.
156. V. Herbert and A. Bisio, Synthetic Rubber: A Project That
Had to Succeed , Greenwood Press, Westport, 1985.
157. J. M. Asua, J. Polym. Sci., Part A: Polym. Chem., 2004,
42, 1025–1041.
158. A. Mv. Herk, ed., Chemistry and Technology of Emulsion
Polymerization, Blackwell Publishing, Oxford, 2005.
159. J. M. Asua, ed., Polymeric Dispersions: Principles and
Applications, Kluwer Academic Publishers, Dordrecht,
1997.
160. C.-S. Chern, Principles and Applications of Emulsion
Polymerization, John Wiley & Sons, Inc, Hoboken, 2008.
161. W. Brostow, R. Chiu, I. M. Kalogeras, and
A. Vassilikou-Dova, Mater. Lett., 2008, 62, 3152–3155.
162. V. Mittal, ed., Miniemulsion Polymerization Technology,
John Wiley & Sons, Inc and Scrivener Publishing,
Hoboken,NJ, Salem, 2010.
163. J. Ugelstad, M. S. El-Aasser, and J. W. Wanderhoff,
J. Polym. Sci., Polym. Lett. Ed., 1973, 111, 503–513.
164. I. Capek and C. S. Chern, Adv. Polym. Sci., 2001, 155,
101–165.
165. M. Antonietti and K. Landfester, Prog. Polym. Sci., 2002,
27, 689–757.
166. J. M. Asua, Prog. Polym. Sci., 2002, 27, 1283–1346.
167. C. Schellenberg, C. Auschra, W. Peter, et al ., WO
2005/023878 A1, Ciba SC, 2005.
168. M. Antonietti, R. Basten, and S. Lohmann, Macromol.
Chem. Phys., 1995, 196, 441–466.
169. I. Capek, Adv. Colloid. Interface Sci., 1999, 82, 253–273.
170. I. Capek, Adv. Colloid. Interface Sci., 1999, 80, 85–149.
171. P. Kumar and K. L. Mittal, eds., Handbook of Microemul-
sion Science and Technology, Marcel Dekker, New York,
1999.
172. A. D. Jenkins, R. G. Jones, and G. Moad, Pure Appl.
Chem., 2010, 82, 483–491.
173. M. Szwarc, Nature, 1956, 176, 1168–1169.
174. K. Matyjaszewski and A. H. E. Mueller, Prog. Polym. Sci.,
2006, 31, 1039–1040.
175. A. H. E. Müller and K. Matyjaszewski, eds., Controlled
and Living Polymerizations, Wiley-VCH Verlag GmbH,
Weinheim, 2010.
176. T. Otsu and M. Yoshida, Makromol. Chem., Rapid Com-
mun., 1982, 3, 127–132.
177. T. Otsu, M. Yoshida, and T. Tazaki, Makromol. Chem.,
Rapid Commun., 1982, 3, 133–140.
178. D. A. Shipp, J. Macromol. Sci., Polym. Rev., 2005, C45,
171–194.
179. D. H. Solomon, J. Polym. Sci., Part A: Polym. Chem., 2005,
43, 5748–5764.
180. K. Matyjaszewski and J. Spanswick, Mater. Today, 2005,
8, 26–33.
181. W. A. Braunecker and K. Matyjaszewski, Prog. Polym.
Sci., 2007, 32, 93–146.
182. G. Moad, E. Rizzardo, and S. H. Thang, Acc. Chem. Res.,
2008, 41, 1133–1142.
183. O. Jung Kwon, J. Polym. Sci., Part A: Polym. Chem., 2008,
46, 6983–7001.
Encyclopedia of Radicals in Chemistry, Biology and Materials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Radicals in Chemistry, Biology and Materials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470971253.rad080
35
184. M. F. Cunningham, Prog. Polym. Sci., 2008, 33, 365–398.
185. S. Yamago, Chem. Rev., 2009, 109, 5051–5068.
186. F. di Lena and K. Matyjaszewski, Prog. Polym. Sci., 2010,
35, 959–1021.
187. M. Destarac, Macromol. React. Eng., 2010, 4, 165–179.
188. J. L. Hodgson, L. B. Roskop, M. S. Gordon, et al ., J. Phys.
Chem. A, 2010, 114, 10458–10466.
189. V. Sciannamea, R. Jerome, and C. Detrembleur, Chem.
Rev., 2008, 108, 1104–1126.
190. A. Kramer and P. Nesvadba, US 6353107 B1, Ciba SC,
2002.
191. P. Nesvadba and A. Kramer, M.-O. Zink, US 6479608 B1,
Ciba SC, 2002.
192. H. Fischer, A. Kramer, S. R. A. Marque, and P. Nesvadba,
Macromolecules, 2005, 38, 9974–9984.
193. S. Miele, P. Nesvadba, and A. Studer, Macromolecules,
2009, 42, 2419–2427.
194. P. Nesvadba, L. Bugnon, and R. Sift, J. Polym. Sci., Part
A: Polym. Chem., 2004, 42, 3332–3341.
195. C. Wetter, J. Gierlich, C. A. Knoop, et al ., Chem.— Eur.
J., 2004, 10, 1156–1166.
196. K. Sakai, K.-I. Yamada, T. Yamasaki, et al ., Tetrahedron,
2010, 66, 2311–2315.
197. C. Auschra, E. Eckstein, R. Knischka, and P. Nesvadba,
Asia Pac. Coat. J., 2003, 16, 20–23.
198. C. Auschra, E. Eckstein, A. Muehlebach, et al ., Prog. Org.
Coat., 2002, 45, 83–93.
199. C. Auschra, E. Eckstein, R. Knischka, et al ., Eur. Coat. J.,
2004, 26, 31–32, 34–35.
200. C. Auschra, E. Eckstein, R. Knischka, et al ., Eur. Coat. J.,
2005, 156, 158, 160, 162–163.
201. F. O. H. Pirrung and C. Auschra, Polym. Prepr., 2005, 46,
316–317.
202. F. Pirrung and C. Auschra, Polymeric dispersants, in
Macromolecular Engineering, eds. K. Matyjaszewski,
Y. Gnanou, and L. Leibler, Wiley-VCH Verlag GmbH,
Weinheim 2007, vol. 4, pp. 2135–2180.
203. A. T. Termaten, M. van der Sluis, F. Pirrung, and
C. Auschra, Polym. Prepr., 2008, 49, 353–354.
204. C. Le Mercier, J. F. Lutz, S. Marque, et al ., Use of
Phosphonylated Nitroxides and Alkoxyamines in Con-
trolled/”Living” Radical Polymerization, ACS Sympo-
sium Series, American Chemical Society, Washington, DC,
2000, vol. 768, pp. 108–122.
205. J. Marchand, L. Autissier, Y. Guillaneuf, et al ., Aust. J.
Chem., 2010, 63, 1237–1244.
206. Arkema. BlocBuilder, http://www.arkema-inc.com/index.
cfm?pag=1257. (accessed 14 July 2011).
207. J. Nicolas, B. Charleux, O. Guerret, and S. Magnet,
Macromolecules, 2004, 37, 4453–4463.
208. D. Gigmes, J. Vinas, N. Chagneux, et al ., SG1 and
BLOCBUILDER technology: a versatile toolbox for the
elaboration of complex macromolecular architectures,
Controlled/Living Radical Polymerization: Progress in
RAFT, DT, NMP & OMRP , ACS Symposium Series,
American Chemical Society, Washington, DC, 2009,
vol. 1024, pp. 245–262.
209. P. Gerard, L. Couvreur, S. Magnet, et al ., Controlled
architecture polymers at Arkema: synthesis, morphol-
ogy and properties of all-acrylic block copolymers, Con-
trolled/Living Radical Polymerization: Progress in RAFT,
36 POLYMERS AND MATERIALS

DT, NMP & OMRP , ACS Symposium Series, Ameri- 237. K. Matyjaszewski, W. Jakubowski, K. Min, et al ., Proc.
can Chemical Society, Washington, DC, 2009, vol. 1024, Natl. Acad. Sci. U.S.A., 2006, 103, 15309–15314.
pp. 361–373. 238. L. Mueller and K. Matyjaszewski, Macromol. React. Eng.,
210. Y. Guillaneuf, D. Gigmes, S. R. A. Marque, et al ., 2010, 4, 180–185.
Macromolecules, 2007, 40, 3108–3114. 239. N. Chan, M. F. Cunningham, and R. A. Hutchinson,
211. B. Charleux, J. Nicolas, and O. Guerret, Macromolecules, Macromol. React. Eng., 2010, 4, 369–380.
2005, 38, 5485–5492. 240. V. Percec, T. Guliashvilli, J. S. Ladislaw, et al ., J. Am.
212. J. Nicolas, S. Brusseau, and B. Charleux, J. Polym. Sci., Chem. Soc., 2006, 128, 14156–14165.
Part A: Polym. Chem., 2010, 48, 34–47. 241. B. M. Rosen and V. Percec, Chem. Rev., 2009, 109,
213. B. Lessard, E. J. Y. Ling, M. S. T. Morin, and 5069–5119.
M. Maric, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 242. X. Jiang, B. M. Rosen, and V. Percec, J. Polym. Sci., Part
1033–1045. A: Polym. Chem., 2010, 48, 403–409.
214. J. Nicolas, B. Charleux, and S. Magnet, J. Polym. Sci., Part 243. S. Fleischmann, B. M. Rosen, and V. Percec, J. Polym.
A: Polym. Chem., 2006, 44, 4142–4153. Sci., Part A: Polym. Chem., 2010, 48, 1190–1196.
215. M. Save, Y. Guillaneuf, and R. G. Gilbert, Aust. J. Chem., 244. Controlled radical polymerization consortium at
2006, 59, 693–711. Carnegie Mellon University, http://www.chem.cmu.
216. B. Charleux and J. Nicolas, Polymer, 2007, 48, edu/groups/maty/crp/. (accessed 14 July 2011).
5813–5833. 245. ATRP Solutions, http://www.atrpsolutions.com/. (accessed
217. P. B. Zetterlund, Y. Kagawa, and M. Okubo, Chem. Rev., 14 July 2011).
2008, 108, 3747–3794. 246. Warwick Effect Polymers, http://www.warwickeffect
218. J. K. Oh, J. Polym. Sci., Part A: Polym. Chem., 2008, 46, polymers.co.uk/. (accessed 14 July 2011).
6983–7001. 247. S. Perrier and C. Barner-Kowollik, J. Polym. Sci., Part A:
219. C. Dire, S. Magnet, L. Couvreur, and B. Charleux, Polym. Chem., 2008, 46, 5715–5723.
Macromolecules, 2009, 42, 95–103. 248. C. Barner-Kowollik, ed., Handbook of RAFT Polymeriza-
220. T. E. Enright, M. F. Cunningham, and B. Keoshkerian, tion, Wiley-VCH Verlag GmbH, Weinheim, 2008.
Macromol. React. Eng., 2010, 4, 186–196. 249. G. Moad, Aust. J. Chem., 2006, 59, 661–662.
221. P. B. Zetterlund, Macromol. Theory Simul., 2010, 19, 250. A. B. Lowe and C. L. McCormick, Prog. Polym. Sci., 2007,
11–23. 32, 283–351.
222. D.-L. Versace, J. Lalevee, J.-P. Fouassier, et al ., Macro- 251. G. Moad, E. Rizzardo, and S. H. Thang, Polym. Int., 2011,
mol. Rapid Commun., 2010, 31, 1383–1388. 60, 9–25.
223. J.-P. Gillet, O. Guerret, and P. Tordo, WO 2000/040526 252. G. Moad, E. Rizzardo, and S. H. Thang, Aust. J. Chem.,
A2, Elf Atochem, 2000. 2009, 62, 1402–1472.
224. O. Guerret, J.-L. Couturier, and C. Le Mercier, WO 253. S. Perrier and P. Takolpuckdee, J. Polym. Sci., Part A:
2002/048159 A1, Atofina, 2002. Polym. Chem., 2005, 43, 5347–5393.
225. D. Benoit, V. Chaplinski, R. Braslau, and C. J. Hawker, 254. H. Willcock and R. K. O’Reilly, Polym. Chem., 2010, 1,
J. Am. Chem. Soc., 1999, 121, 3904–3920. 149–157.
226. D. A. Tirrell, J. Polym. Sci., Part A: Polym. Chem., 1998, 255. M. Semsarilar and S. Perrier, Nat. Chem., 2010, 2,
36, 2667–2668. 811–820.
227. P. Nesvadba, Chimia, 2006, 60, 832–840. 256. M. Destarac, Polym. Prepr., 2008, 49, 179–180.
228. D. Bertin, D. Gigmes, and S. R. A. Marque, Recent Res. 257. M. Destarac, S. Deroo, H. Lannibois-Drean, et al .,
Dev. Org. Chem., 2006, 10, 63–121. MADIX technology: from innovative concepts to indus-
229. A. C. Greene and R. B. Grubbs, Current methods trialization of block copolymers for emulsion stabiliza-
for N -alkoxyamine synthesis, Controlled/Living Radical tion, Controlled/Living Radical Polymerization: Progress
Polymerization: Progress in RAFT, DT, NMP & OMRP , in RAFT, DT, NMP & OMRP , ACS Symposium Series,
ACS Symposium Series, American Chemical Society, American Chemical Society, Washington, DC, 2009,
Washington, DC, 2009, vol. 1024, pp. 81–93. vol. 1024, pp. 347–359.
230. J.-L. Couturier, WO 2009/010693 A2, Arkema, 2009. 258. G. David, C. Boyer, J. Tonnar, et al ., Chem. Rev., 2006,
231. H.-J. Kirner, F. Schwarzenbach, P. A. van der Schaaf, 106, 3936–3962.
et al ., Adv. Synth. Catal., 2004, 346, 554–560. 259. J. Scheirs and D. Priddy, eds., Modern Styrenic Polymers,
232. Y. Guillaneuf, P.-E. Dufils, L. Autissier, et al ., Macro- John Wiley & Sons, Ltd, Chichester, 2003.
molecules, 2009, 43, 91–100. 260. S. G. Patrick, Practical Guide to Polyvinyl Chloride, Rapra
233. Y. Shen, H. Tang, and S. Ding, Prog. Polym. Sci., 2004, Technology, Shawbury, 2005.
29, 1053–1078. 261. D. Braun, J. Polym. Sci., Part A: Polym. Chem., 2004, 42,
234. W. Jakubowski and K. Matyjaszewski, Angew. Chem. Int. 578–586.
Ed., 2006, 45, 4482–4486. 262. C. Vasile and M. Pascu, Practical Guide to Polyethylene,
235. N. V. Tsarevsky and K. Matyjaszewski, Chem. Rev., 2007, Rapra Technology, Shawbury, 2005.
107, 2270–2299.
236. R. Nicolay, Y. Kwak, and K. Matyjaszewski, Angew.
Chem. Int. Ed., 2010, 49, 541–544.

Encyclopedia of Radicals in Chemistry, Biology and Materials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Radicals in Chemistry, Biology and Materials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470971253.rad080